TWI521302B - Resist composition and method for producing resist pattern - Google Patents

Description

Method for producing resist composition and resist pattern

The present invention relates to a resist composition and a method of producing a resist pattern.

In the past, various photolithography techniques have been actively studied to use short-wavelength light (for example, ArF excimer laser (wavelength 193 nm)) as an exposure light source as semiconductor micromachining. A resist composition for use in such photolithography technology is described in the patent document WO 2007/116664, which contains a compound represented by the formula (A), a compound represented by the formula (B), and a formula (C). a polymer obtained by polymerizing a compound; a polymer obtained by polymerizing a compound represented by the formula (B) and a compound represented by the formula (D); p-cyclohexylphenyldiphenylphosphonium perfluorobutanesulfonic acid as an acid generator Salt; and solvent.

However, with such conventional resist compositions, the focus limit (DOF) at the time of fabricating the resist pattern, the mask error factor (MEF) of the obtained resist pattern may be unsatisfactory, and the resist composition The number of defects in the resist pattern produced may increase significantly.

The present invention provides the following invention.

<1> A resist composition comprising: a resin having a structural unit derived from a compound represented by the formula (a); and an acid generator,

Wherein R ¹ represents a hydrogen atom or a methyl group; R ² represents an optionally substituted C ₁ to C ₁₈ aliphatic hydrocarbon group; and A ¹ represents an optionally substituted C ₁ to C ₆ alkaneyi group or formula (a) -g1) the base shown;

Wherein s represents 0 or 1; A ¹⁰ and A ¹² independently represent an optionally substituted C ₁ to C ₅ aliphatic hydrocarbon group; A ¹¹ represents a single bond or an optionally substituted C ₁ to C ₅ aliphatic hydrocarbon group; X ¹⁰ And X ¹¹ independently represents an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group; however, the total number of carbon atoms of A ¹⁰ , A ¹¹ , A ¹² , X ¹⁰ and X ¹¹ is 6 or less.

<2> The resist composition according to <1>, which further comprises a solvent.

<3> A method for producing a resist pattern having the following steps;

(1) applying the resist composition according to <1> to a substrate;

(2) drying the applied composition to form a composition layer;

(3) exposing the composition layer using an exposure device;

(4) heating the exposed composition layer;

(5) Developing the heated composition layer using a developing device.

Further, the present invention also provides the following inventions and the like.

<4> The resist composition according to <1> or <2>, wherein the acid generator is a salt represented by the formula (B1).

Wherein Q ¹ and Q ² independently represent a fluorine atom or a C ₁ to C ₆ perfluoroalkyl group; L ^b1 represents an optionally substituted C ₁ to C ₁₇ divalent aliphatic hydrocarbon group, and -CH contained in the aliphatic hydrocarbon group ₂ - may be -O- or -CO-substituted; Y represents a C ₁ to C ₁₈ aliphatic hydrocarbon group optionally substituted and -CH ₂ - may -O-, -CO- or -SO ₂ - contained in the aliphatic hydrocarbon group Substitution; and Z ⁺ represents an organic cation.

<5> The resist composition according to <1>, <2> or <4>, wherein A ¹ of the compound (a) is a C ₁ to C ₆ alkanediyl group.

<6> The <1>, <2>, <4> and a <5> in the resist composition according to any one of a, wherein, A compound (a) is ^an extension of ethyl.

The resist composition according to any one of <1>, wherein R ² of the compound (a) is an aliphatic hydrocarbon group having a halogen atom.

The resist composition according to any one of <1>, wherein the R ² of the compound (a) is a C ₁ to C ₃ perfluoroalkyl group. .

The resist composition according to any one of <1>, wherein R ² of the compound (a) is a group represented by the formula (a-g2). .

-A ¹³ -X ¹² -A ¹⁴ (a-g2)

Wherein A ¹³ represents a C ₃ to C ₁₇ aliphatic hydrocarbon group having a halogen atom as needed; X ¹² represents a carbonyloxy group or an oxycarbonyl group; and A ¹⁴ represents a C ₃ to C ₁₇ aliphatic hydrocarbon group having a halogen atom as needed; The total number of carbon atoms of A ¹³ , A ¹⁴ and X ¹² is 18 or less.

<10> The resist composition according to <9>, wherein, in the formula (a-g2), A ¹³ is an aliphatic hydrocarbon group having a halogen atom or A ¹⁴ is an aliphatic hydrocarbon group having a halogen atom.

<11> The resist composition according to <9>, wherein, in the formula (a-g2), A ¹⁴ is an alicyclic hydrocarbon group having a halogen atom as necessary.

<12> The resist composition according to any one of <1>, wherein the R ² of the compound (a) is as follows;

The resist composition according to any one of <1>, wherein the Y is a C ₁ to C ₁₈ alicyclic hydrocarbon group which is optionally substituted.

<14> a compound of the formula (a'),

Wherein R ¹ represents a hydrogen atom or a methyl group; A ¹ represents a C ₁ to C ₆ alkanediyl group optionally substituted or a group represented by the formula (a-g1)

Wherein s represents 0 or 1; A ¹⁰ and A ¹² independently represent an optionally substituted C ₁ to C ₅ aliphatic hydrocarbon group; A ¹¹ represents a single bond or an optionally substituted C ₁ to C ₅ aliphatic hydrocarbon group; X ¹⁰ And X ¹¹ independently represents an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group; however, the total number of carbon atoms of A ¹⁰ , A ¹¹ , A ¹² , X ¹⁰ and X ¹¹ is 6 or less; A ¹³ represents as needed a C ₃ to C ₁₇ aliphatic hydrocarbon group of a halogen atom; X ¹² represents a carbonyloxy group or an oxycarbonyl group; and A ¹⁴ represents a C ₃ to C ₁₇ aliphatic hydrocarbon group having a halogen atom as needed; however, a carbon atom of A ¹³ and A ¹⁴ The total number is 17 or less.

<15> The compound according to <14>, wherein, in the formula (a'), A ¹³ is an aliphatic hydrocarbon group having a halogen atom.

<16> The compound according to <14> or <15>, wherein, in the formula (a'), A ¹⁴ is an alicyclic hydrocarbon group which has a halogen atom as needed.

<17> The compound according to <14>, wherein the structure represented by the formula *-A ¹³ -X ¹² -A ^{14 in} the formula (a') is as follows (* represents a bond to a carbonyl bond) );

<18> A resin having a structural unit derived from the compound of <14> to <17>.

According to the resist composition of the present invention, when a resist pattern is produced, a resist pattern having an excellent DOF (wide DOF) and an excellent MEF can be produced, and there are fewer defects in the pattern.

<Resist composition>

The resist composition of the present invention contains: a resin (hereinafter may be referred to as "resin (A)"), and an acid generator (hereinafter may be referred to as "acid generator (B)").

Further, if necessary, the resist composition may contain a solvent as well as an additive such as a basic compound which is regarded as a quencher in the art.

<Resin (A)>

The resin (A) has a structural unit derived from a compound represented by the formula (a) (hereinafter may be referred to as "compound (a)").

<compound (a)>

Wherein R ¹ represents a hydrogen atom or a methyl group; R ² represents an optionally substituted C ₁ to C ₁₈ aliphatic hydrocarbon group; and A ¹ represents an optionally substituted C ₁ to C ₆ alkanediyl group or a formula (a-g1); Base (hereinafter may be referred to as "(a-g1) base");

Wherein s represents 0 or 1; A ¹⁰ and A ¹² independently represent an optionally substituted C ₁ to C ₅ aliphatic hydrocarbon group; A ¹¹ represents a single bond or an optionally substituted C ₁ to C ₅ aliphatic hydrocarbon group; X ¹⁰ And X ¹¹ independently represents an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group; however, the total number of carbon atoms of A ¹⁰ , A ¹¹ , A ¹² , X ¹⁰ and X ¹¹ is 6 or less.

The alkanediyl group of A ¹ may be a linear or branched alkanediyl group. Examples of alkanediyl groups include linear alkanediyl groups such as methylene, ethyl, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, pentyl Alkan-1,5-diyl, pentane-1,4-diyl, hexane-1,6-diyl and hexane-1,5-diyl; branched alkanediyl such as 1-methyl- 1,3-propanyl, 2-methyl-1,3-propanyl, 2-methyl-1,2-propanyl, 1-methyl-1,4-butyl and 2-methyl Base-1,4-butylene.

Examples of the substituent of the alkanediyl group include a hydroxyl group and a C ₁ to C ₆ alkoxy group.

Examples of the (a-g1) group containing an oxygen atom include the ones shown below. In the following formula, the base system is represented by the two sides of the corresponding formula (a), that is, the left side of the base is bonded to -O- on the R ¹ side and the right side of the base is bonded to the R ² side. -O-, * indicates the bond.

Examples of (a-g1) groups containing a carbonyl group include the ones shown below.

Examples of the (a-g1) group containing a carbonyloxy group include the ones shown below.

Examples of the (a-g1) group containing an oxycarbonyl group include the ones shown below.

Among these, A ^{1 is} preferably an alkanediyl group, more preferably an unsubstituted alkanediyl group, still more preferably a C ₁ to C ₄ alkanediyl group, and most preferably an extended ethyl group.

The aliphatic hydrocarbon group of R ² may include a carbon-carbon double bond, however, a saturated aliphatic hydrocarbon group is preferred. The saturated aliphatic hydrocarbon group of R ² may be a linear or branched alkyl group, an alicyclic hydrocarbon group, and a combination of these.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.

Examples of the alicyclic hydrocarbon group include monocyclic hydrocarbon groups such as cycloalkyl groups such as cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl and cyclooctyl; and polycyclic hydrocarbon groups such as decalin Decahydronaphtyl, adamantyl, norbornyl (i.e., bicyclo [2.2.1] hexyl), methylnorbornyl, and the following.

R ² may be a substituted or unsubstituted aliphatic hydrocarbon group, and a substituted aliphatic hydrocarbon group is preferred.

Examples of the substituent of R ² preferably include a halogen atom or a group represented by the formula (a-g3) (hereinafter may be referred to as "(a-g3) group").

-X ^12' -A ¹⁴ (a-g3)

Wherein X ^{12 '} represents an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group: A ¹⁴ represents a C ₃ to C ₁₇ aliphatic hydrocarbon group having a halogen atom as needed.

Examples of the aliphatic hydrocarbon group having a halogen atom of R ² include an alkyl group substituted with a halogen atom and an alicyclic hydrocarbon group substituted with a halogen atom (preferably a cycloalkyl group substituted with a halogen atom).

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom is preferred.

The perfluoroalkyl group constituting all hydrogen atoms of the alkyl group is substituted by a halogen atom, and the perfluorocycloalkyl group constituting all hydrogen atoms of the cycloalkyl group is substituted by a halogen atom, so that when the aliphatic hydrocarbon group in R ² has a halogen The atom is better. Among these, a perfluoroalkyl group is preferred, a C ₁ to C ₆ perfluoroalkyl group is preferred, and a C ₁ to C ₃ perfluoroalkyl group is more preferred.

Examples of perfluoroalkyl groups include trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluoroheptyl, and perfluorooctyl.

X ^{12 ' is} preferably a carbonyloxy group or an oxycarbonyl group.

In the compound (a), R ² is an aliphatic hydrocarbon group substituted by a fluorine atom, and A ¹ is an exoethyl group, and includes a compound represented by the following formula (a1) to formula (a22).

In the compound (a), R ² is a corresponding formula (a3), (a4), (a7), (a8), (a11), (a12), (a15), (a16), (a19), (a20), a perfluoroalkyl or perfluorocycloalkyl group of the compound of (a21) and (a22).

When the aliphatic hydrocarbon group of R ² is substituted with an (a-g3) group, the number of (a-g3) groups may be 1 or more. In any case, the total number of carbon atoms of R ² substituted by the (a-g3) group is preferably 15 or less, more preferably 12 or less. Therefore, it is preferred to substitute R ² via an (a-g3) group.

Therefore, R ^{2 is} preferably a group represented by the following formula (a-g2) (hereinafter may be referred to as "(a-g2) group").

-A ¹³ -X ¹² -A ¹⁴ (a-g2)

Wherein A ¹³ represents a C ₃ to C ₁₇ aliphatic hydrocarbon group having a halogen atom as needed; X ¹² represents a carbonyloxy group or an oxycarbonyl group; and A ¹⁴ represents a C ₃ to C ₁₇ aliphatic hydrocarbon group having a halogen atom as needed; The total number of carbon atoms of A ¹³ , A ¹⁴ and X ¹² is 18 or less.

Preferred examples of the (a-g2) group include the following groups. * indicates a bond to a carbonyl group.

In the compound (a), R ² is an aliphatic hydrocarbon group substituted with one (a-g3) group, that is, R ² is an (a-g2) group, which is represented by the formula (a'), and may be referred to as "hereinafter". Compound (a')".

Wherein A ¹³ represents a C ₃ to C ₁₇ aliphatic hydrocarbon group having a halogen atom as needed; X ¹² represents a carbonyloxy group or an oxycarbonyl group; and A ¹⁴ represents a C ₃ to C ₁₇ aliphatic hydrocarbon group having a halogen atom as needed; The total number of carbon atoms of A ¹³ and A ¹⁴ is 17 or less; and A ¹ and R ¹ are the same as defined above.

The compound (a') is an effective and novel manufacturing material for the resin (A) for producing the resist composition of the present invention. Accordingly, the present invention includes the invention according to the compound (a').

In the compound (a'), both of A ¹³ and A ^{14 may} be a group having a halogen atom, but it is preferred that only one of them is an aliphatic hydrocarbon group having a halogen atom. Among these, it is preferred that only A ¹³ is a group having a halogen atom, particularly preferably A ¹³ is an alkanediyl group having a fluorine atom, and more preferably A ¹³ is a perfluoroalkanediyl group.

In the compound (a'), R ² is a perfluoroalkanediyl group and A ¹ is an exoethyl group, and includes a compound represented by the following formula (a'1) to formula (a'46).

Among these, a compound represented by the formula (a'7) to the formula (a'42) is preferred.

The total number of carbon atoms of A ¹³ and A ¹⁴ may be selected from 17 or less, the number of carbon atoms of A ¹³ is preferably from 1 to 6, and more preferably from 1 to 3, and the number of carbon atoms of A ¹⁴ is preferably from 4 to 15, and 5 to 12 are better. Among these, A ^{14 is} preferably a C ₆ to C ₁₂ alicyclic hydrocarbon group, and more preferably a cyclohexyl group or an adamantyl group.

The compound (a) can be produced by the methods (1) to (3) below.

(1) The compound of the formula (a) can be obtained by reacting a compound represented by the formula (as-1) with a compound of the formula (as-2) in the presence of a base catalyst.

Wherein R ¹ , R ² and A ¹ have the same definitions as described above.

This reaction is usually carried out in a solvent. An example of the basic catalyst preferably includes pyridine. Examples of the solvent preferably include tetrahydrofuran.

As the compound represented by the formula (as-1), a commercially available product or a product produced according to a known method can be used.

A known method is, for example, a method of condensing (meth)acrylic acid or a derivative (for example, (meth)acrylofluorene chloride) with a suitable diol (HO-A ¹ -OH). Examples of commercially available products include hydroxyethyl methacrylate and hydroxybutyl methacrylate.

As the compound represented by the formula (as-2), a compound which converts a carboxylic acid into an acid anhydride corresponding to the kind of R ² can be used. Examples of commercially available products include heptafluoroisobutyric anhydride.

(2) Compound (a) can be produced by the method described in the following scheme.

The compound of the formula (a) can be obtained by reacting a compound represented by the formula (as-3) with a compound represented by the formula (as-4) in the presence or absence of a solvent. A deoxidizer (for example, sodium carbonate) may be allowed to coexist in this reaction. Examples of the solvent preferably include tetrahydrofuran, methyl isobutyl ketone, and toluene.

The compound represented by the formula (as-3) is (meth)acryl chloride, and is a commercially available product. Alternatively, a compound represented by the formula (as-3) in which a chlorine atom is substituted with a bromine atom or an iodine atom can be used instead of the compound represented by the formula (as-3). The compound of the formula (as-3) wherein the chlorine atom is replaced by a bromine atom or an iodine atom can be produced by reacting (meth)acrylic acid with a brominating agent or an iodinating agent.

The compound of the formula (as-4) can be a carboxylic acid (for example, R ² -COOH) or a derivative (for example, R ² -COCl) as a suitable diol (HO-A ¹ - by the kind corresponding to R ² ). Obtained by condensation of OH).

(3) The compound (a) can be produced by the method described in the following scheme.

The compound of the formula (a) can be obtained by reacting a compound represented by the formula (as-1) with a compound represented by the formula (as-5).

Examples of the compound represented by the formula (as-1) include the same as defined above.

The carboxylic acid represented by the formula (as-5) can be produced by a known method depending on the kind of R ² . When the compound of the formula (a') is produced, the following compounds can be used.

The reaction of the compound of the formula (as-1) with the carboxylic acid of the formula (as-5) is usually carried out in a solvent. Examples of the solvent preferably include tetrahydrofuran and toluene. A known esterifying agent (for example, an acid catalyst and a carbodiimide catalyst) may be allowed to coexist in the reaction.

The ratio of the structural unit derived from the compound (a) in the resin (A) is usually from 1 to 100 mol%, preferably from 5 to 95 mol, based on all the structural units (100 mol%) constituting the resin (A). % of ear, and more preferably 10 to 90% by mole.

In order to make the ratio of the structural unit derived from the compound (a) in the resin (A) in the above range, the amount of the compound (a) used can be adjusted with respect to the total amount of the monomers used in the production of the resin (A) (below All need to adjust the proportion). When the resin (A) is produced, the compound (a) may be used as a single compound or as a mixture of two or more compounds.

The resist composition of the present invention is preferably a resist composition which can form a resist pattern by a synergistic effect of a resin and an acid generator (B). Therefore, the resin (A) is preferably insoluble or poorly soluble in an aqueous alkaline solution, and can be converted into a resin dissolved in an alkaline aqueous solution by the action of an acid. Such a resin having such a property and having a structural unit derived from the compound (a) may hereinafter be referred to as "resin (AA)".

Here, "converting into a resin dissolved in an alkaline aqueous solution by the action of an acid" means that the resin before contact with the acid is insoluble or poorly soluble in the alkaline aqueous solution, and becomes soluble in the alkaline aqueous solution upon contact with the acid.

Thus, the resin (AA) contains a hydrophilic group in which at least a portion is protected by a protecting group which can be deprotected by the action of an acid, and preferably all of the hydrophilic groups are protected by a protecting group. These protecting groups can be deprotected by the action of an acid, and the resin (AA) will be converted into a resin which can be dissolved in an aqueous alkaline solution. Hereinafter, the hydrophilic group protected by the protecting group may be referred to as "acid labile group". Examples of the acid labile group include a hydroxyl group and a carboxyl group, and a carboxyl group is preferred. That is, the "acid-labile group" is contacted with an acid to cut off a radical (i.e., a protecting group) and to generate a group having a hydrophilic group such as a carboxyl group or a hydroxyl group. The resin (AA) can be produced by polymerizing the compound (a) with a monomer having an acid labile group.

In the resist composition of the present invention, the resin (A) itself may not necessarily have the above properties. These resins having structural units derived from the compound (a) but having no such properties may be referred to as "resin (AB)" hereinafter.

By containing a resin (AA) and/or a resin (AB) in the resist composition, the composition produces an excellent mask error factor (MEF) and a wide focus limit (DOF) when a resist pattern is formed. And a resist pattern having fewer defects can be formed from the resist composition.

The resin (A) preferably has a structural unit derived from the following monomers or known monomers.

In the present specification, any of the groups listed below may be applied to any of the chemical formulas having a similar group, and the similar groups may have a carbon number as desired, unless otherwise specified. Unless otherwise specified, if a group can be a straight chain and a branched chain and/or a cyclic structure, all structures can be included in a group and can exist simultaneously. In the case of stereoisomeric forms, all stereoisomeric forms are included. Each base may be a monovalent, or a divalent or higher basis, depending on the bonding position and the bonding form.

The hydrocarbon group includes an aliphatic hydrocarbon group as well as an aromatic group. The aliphatic hydrocarbon group includes a chain aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and combinations thereof. The aliphatic hydrocarbon group may include a carbon-carbon double bond, however, a saturated aliphatic hydrocarbon group is preferred.

Examples of the monovalent chain aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, a hexadecyl group, a fifteen group, and a tenth Hexyldecyl, heptadecyl and octadecyl. The aliphatic hydrocarbon group may be any of a linear or branched aliphatic hydrocarbon group.

Examples of the divalent chain aliphatic hydrocarbon group include a group in which a hydrogen atom is removed from the above monovalent chain aliphatic hydrocarbon group.

The cycloaliphatic hydrocarbon group may be any of a monocyclic or polycyclic aliphatic hydrocarbon group. The cycloaliphatic hydrocarbon may be referred to as "alicyclic hydrocarbon group" hereinafter.

Examples of the monovalent alicyclic hydrocarbon group include a group in which a hydrogen atom is removed from the alicyclic hydrocarbon. Examples of the divalent alicyclic hydrocarbon group include a group derived from two hydrogen atoms of an alicyclic hydrocarbon group.

Examples of the alicyclic hydrocarbon typically include the following cyclic hydrocarbons.

Examples of the aromatic hydrocarbon group typically include an aromatic group such as a phenyl group, a naphthyl group, an anthracenyl group, a biphenyl group, a phenanthryl group, and an anthracenyl group.

The aliphatic hydrocarbon group and the aromatic hydrocarbon group may be substituted with a substituent.

Typical examples of the substituent of the aliphatic hydrocarbon group include a halogen atom, an alkoxy group, an alkylthio group, a decyl group, an aryl group, an aralkyl group, and an aryloxy group.

Typical examples of the substituent of the aromatic hydrocarbon group include a halogen atom, an alkoxy group, an alkylthio group, a decyl group, an alkyl group, and an aryloxy group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a decyloxy group, and a dodecyloxy group. The alkoxy group may be any of a linear or branched alkoxy group.

Examples of the alkylthio group include a group in which an oxygen atom in the alkoxy group is substituted by a sulfur atom.

Examples of fluorenyl groups include a group that binds a carbonyl group to an alkyl group, such as an ethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group, a pentamyl group, a hexyl carbonyl group, a heptyl carbonyl group, an octylcarbonyl group, a fluorenylcarbonyl group, and a dodecylcarbonyl group: Binding to a carbonyl to aryl group. The alkyl group in the fluorenyl group may be any of a linear or branched alkyl group.

Examples of the aryloxy group include a group which bonds an oxygen atom to an aryl group.

Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, and a naphthylethyl group.

Examples of aryl groups and alkyl groups include the same definitions as described above.

"(Meth)acrylic monomer" means that at least one monomer has a structure of "CH ₂ =CH-CO-" or "CH ₂ =C(CH ₃ )-CO-", "(meth)acrylate" and "(Meth)acrylic acid" means "at least one acrylate or methacrylate" and "at least one acrylic acid or methacrylic acid", respectively.

<monomer (a1)>

The monomer having an acid labile group may hereinafter be referred to as "monomer (a1)". When the hydrophilic group is a carboxyl group, examples of the acid labile group include a group in which a hydrogen atom of a carboxyl group (ie, -COOH) is substituted with an organic group and an atom of -O- bonded to a carboxyl group in the organic group is a tertiary carbon atom. The basis.

Among such acid labile groups, preferred examples thereof include the group represented by the following formula (1). Hereinafter, the group represented by the formula (1) may be referred to as "acid-labile group (1)".

Wherein R ^a1 to R ^a3 independently represent a C ₁ to C ₈ aliphatic hydrocarbon group or R ^a1 and R ^a2 may be bonded to each other by a carbon atom bonded to R ^a1 and R ^a2 to form a C ₃ to C ₂₀ ring, including The aliphatic hydrocarbon group or at least one -CH ₂ - of the ring may be replaced by -O-, -S- or -CO-, and * represents a bond.

Examples of the aliphatic hydrocarbon group of R ^a1 to R ^a3 include an alkyl group and an alicyclic hydrocarbon group.

Examples of alkyl groups, including methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, t-butyl, isobutyl, n-pentyl, isopentyl, third amyl , neopentyl, 1-methylbutyl, 2-methylbutyl, n-hexyl, 1-methylpentyl, 1,2-dimethylpropyl, and 1-ethylpropyl. Among these, the alkyl group preferably has 1 to 8 carbon atoms.

Examples of the alicyclic hydrocarbon group include a monocyclic or polycyclic saturated hydrocarbon group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group; and a polycyclic hydrocarbon group such as decahydronaphthyl group, King Kong An alkyl group, a thiol group (i.e., a bicyclo [2.2.1] hexyl group), and a methylnorbornyl group, and a group as defined below.

When R ^a1 and R ^{a2 are} bonded to each other to form a ring, an example of a -C(R ^a1 )(R ^a2 )(R ^a3 ) group includes the following groups.

The ring preferably has from 3 to 12 carbon atoms.

Specific examples of the acid labile group include, for example, a 1,1-dialkylalkoxycarbonyl group (in the formula (1), R ^a1 to R ^a3 are an alkyl group, preferably a third butoxycarbonyl group), 2 -alkyladamantan-2-yloxycarbonyl (in formula (1), R ^a1 , R ^a2 and a carbon atom form an adamantyl group, and R ^a3 is an alkyl group), and 1-(diamantine-1) -yl)-1-alkylalkoxycarbonyl (in the formula (1), R ^a1 and R ^a2 are alkyl groups, and R ^a3 is adamantyl).

When the hydrophilic group is a hydroxyl group, examples of the acid labile group include a group in which a hydrogen atom of a hydroxyl group is substituted with an organic group and results in an acetal structure. Among such acid labile groups, preferred examples thereof include a group represented by the following formula (2). Hereinafter, the group represented by the formula (2) may be referred to as "acid-labile group (2)".

Wherein, R ^b1 and R ^{b2 may} independently represent a hydrogen atom or a C ₁ to C ₁₂ hydrocarbon group, R ^b3 represents a C ₁ to C ₂₀ hydrocarbon group, or R ^b2 and R ^b3 may be bonded to a carbon of R ^b2 and R ^b3 The atoms and oxygen atoms combine with each other to form a C ₃ to C ₂₀ ring. One or more -CH ₂ - contained in the hydrocarbon group and the ring may be replaced by -O-, -S- or -CO-, and * represents a bond.

The hydrocarbon group of R ^b1 to R ^b3 includes any of an aliphatic hydrocarbon group and an aromatic hydrocarbon group.

Examples of the aliphatic hydrocarbon group include the same examples as described above.

Examples of the aromatic hydrocarbon group include an aromatic group such as a phenyl group, a naphthyl group, a p-methylphenyl group, a p-tert-butylphenyl group, a p-adamantylphenyl group, a tolyl group, a xylyl group, a cumene group. Cumenyl, 2,4,6-trityl, mebiphenyl, fluorenyl, phenanthryl, 2,6-diethylphenyl, and 2-methyl-6-ethylphenyl.

Examples of the ring formed by bonding R ^b2 and R ^b3 include the same ring as that formed by bonding R ^a1 and R ^a2 .

At least one of R ^b1 and R ^{b2 is} preferably a hydrogen atom.

Specific examples of the acid labile group (2) include the following groups.

The monomer having an acid labile group (a1) is preferably a monomer having an acid labile group and a carbon-carbon double bond, for example, an acid labile group (1) and/or an acid labile group (2) and carbon. a monomer of a carbon double bond, and preferably a (meth)acrylic monomer having an acid labile group, for example, a (meth)acrylic monomer having an acid labile group (1).

Among the (meth)acrylic monomers having an acid labile group (1), preferred are monomers containing an acid labile group having a C ₅ to C ₂₀ alicyclic hydrocarbon group. When the resin (AA) used is obtained by polymerizing a monomer having a large structure such as an alicyclic hydrocarbon group, there is a tendency to obtain a resist composition having an excellent resolution when a resist pattern is produced.

When the (meth)acrylic monomer contains an acid labile group having an alicyclic hydrocarbon group, examples thereof include a monomer represented by the formula (a1-a) (hereinafter may be referred to as "monomer (a1-1)"). .

Wherein R' represents a hydrogen atom or a methyl group; L represents *-O- or *-O-(CH ₂ ) _k1 -CO-O-, k1 represents an integer of 1 to 7, and * represents a bond to a carbonyl group (-CO-) a bond; a ring W represents a C ₅ to C ₂₀ alicyclic hydrocarbon group; R represents a C ₁ to C ₁₀ aliphatic hydrocarbon group; and m1 represents an integer of 0 to 14.

In the formula (a1-a), the alicyclic hydrocarbon group is preferably a C ₅ to C ₁₂ monocyclic ring and a polycyclic hydrocarbon group, and more preferably a C ₅ to C ₁₀ alicyclic hydrocarbon group.

Among the (meth)acrylic monomers having an acid labile group (1) having an alicyclic hydrocarbon group, a monomer having an adamantyl group represented by the formula (a1-1) is preferred. It is referred to as "monomer (a1-1)") and a monomer having a cycloalkyl group represented by the formula (a1-2) (hereinafter may be referred to as "monomer (a1-2)"). These may be used as a single compound or as a mixture of two or more compounds.

Wherein, L ^a1 and L ^a2 independently represent *-O- or *-O-(CH ₂ ) _k1 -CO-O-, k1 represents an integer of 1 to 7, and * represents a bond to a carboxyl group (-CO-) R ^a4 and R ^a5 independently represent a hydrogen atom or a methyl group; R ^a6 and R ^a7 independently represent a C ₁ to C ₁₀ aliphatic hydrocarbon group; and m 1 represents an integer of 0 to 14; n 1 represents an integer of 0 to 10; Represents an integer from 0 to 3.

In the formula (a1-1) and the formula (a1-2), L ^a1 and L ^{a2 are} preferably -O- or *-O-(CH ₂ ) _k1' -CO-O-, where k1' represents The integer is 1 to 4, more preferably -O- or *-O-CH ₂ -CO-O-, and still more preferably -O-.

R ^a4 and R ^{a5 are} preferably a methyl group.

The aliphatic hydrocarbon group of R ^a6 and R ^a7 is preferably a C ₁ to C ₈ alkyl group or a C ₃ to C ₁₀ alicyclic hydrocarbon group, and a C ₁ to C ₈ alkyl group or a C ₃ to C ₈ alicyclic hydrocarbon group. Preferably, it is more preferably a C ₁ to C ₆ alkyl group or a C ₃ to C ₆ alicyclic hydrocarbon group.

M1 is preferably an integer of 9 to 3, and more preferably 0 or 1.

N1 is preferably an integer of 0 to 3, and more preferably 0 or 1.

N1' is preferably 0 or 1, and more preferably 1.

Examples of the monomer (a1-1) include the following groups.

Among these, as the monomer (a1-1), 2-methyladamantan-2-yl (meth)acrylate and 2-ethyladamantan-2-yl (meth)acrylate are preferred. And 2-isopropyladamantan-2-yl (meth)acrylate, and more preferably 2-methyladamantan-2-yl methacrylate or 2-ethyladamantane-2-methacrylate The base ester and 2-isopropyladamantan-2-yl methacrylate are preferred.

Examples of the monomer (a1-2) include the following groups.

Among these, as the monomer (a1-2), 1-ethylcyclohexane-1-(meth)acrylate is preferred, and 1-ethylcyclohexane-1 is more preferred. - a base ester.

When the resin (AA) contains a structural unit derived from the monomer (a1-1) and/or the monomer (a1-2), the total proportion of the resin (AA) is usually 10 to 95 m. %, preferably 15 to 90 mol%, and more preferably 20 to 85 mol%.

The monomer having an acid labile group (1) and a carbon-carbon double bond includes a monomer having a norbornene ring represented by the formula (a1-3). These monomers may hereinafter be referred to as "monomer (a1-3)".

Wherein R ^a9 represents a hydrogen atom, optionally a C ₁ to C ₃ alkyl group having a hydroxyl group, a carboxyl group, a cyano group or —COOR ^a13 , and R ^a13 represents a C ₁ to C ₂₀ aliphatic hydrocarbon group, one or more of which are contained therein. The hydrogen atom may be replaced by a hydroxyl group in which one or more -CH ₂ - may be substituted by -O- or -CO-: R ^a10 to R ^a12 independently represent a C ₁ to C ₂₀ aliphatic hydrocarbon group, or R ^a10 and R ^A11 may be bonded to each other to form a ring in which one or more hydrogen atoms may be replaced by a hydroxyl group or the like, wherein one or more of -CH ₂ - contained may be replaced by -O- or -CO-.

Examples of the alkyl group having a hydroxyl group of R ^a9 include a methylol group, and a 2-hydroxyethyl group.

Examples of the -COOR ^a13 group of R ^a9 include a group in which a carbonyl group is bonded to an alkoxy group, such as a methoxycarbonyl group or an ethoxycarbonyl group.

Examples of the aliphatic hydrocarbon group of R ^a10 to R ^a12 include a methyl group, an ethyl group, a cyclohexyl group, a methylcyclohexyl group, a hydroxycyclohexyl group, a pendant oxycyclohexyl group, and an adamantyl group.

Examples of the ring formed by R ^a10 , R ^a11 and a carbon atom bonded to these include an aliphatic hydrocarbon group such as a cyclohexyl group and an adamantyl group.

Examples of R ^a13 include methyl, ethyl, propyl, 2-sided oxy-oxolane-3-yl and 2-sided oxy-oxolane-4-yl. R ^{13 is} preferably a C ₁ to C ₈ alkyl group or a C ₃ to C ₂₀ alicyclic hydrocarbon group.

Examples of the monomer having a norbornene ring (a1-3) include, for example, 5-butene-2-carboxylate tert-butyl ester, 5-northene-2-carboxylic acid 1-cyclohexyl-1 -methylethyl ester, 5-methylcyclohexene-2-carboxylic acid 1-methylcyclohexyl ester, 5-northene-2-carboxylic acid 2-methyl-2-adamantan-2-yl ester, 5 -nordecene-2-carboxylic acid 2-ethyl-2-adamantan-2-yl ester, 5-northene-2-carboxylic acid 1-(4-methylcyclohexyl)-1-methyl Ester, 5-(4-hydroxycyclohexyl)-1-methylethyl 5-decal-2-carboxylate, 1-methyl-northene-2-carboxylic acid 1-methyl-(4-sideoxy Cyclohexyl)-1-ethyl ester, and 1-(1-adamantan-1-yl)-1-methylethyl 5-decalene-2-carboxylate.

A resin having a structural unit derived from the monomer (a1-3), since it has a large structure, can improve the resolution of the obtained resist composition, and is fixed by being bonded to the main chain of the resin (AA) The norbornene ring can also improve the dry-etching tolerance of the resulting resist composition.

When the resin (A) contains a structural unit derived from a monomer represented by the formula (a1-3), the proportion of the entire structural unit constituting the resin (AA) is usually 10 to 95 mol%, preferably 15 to 90% by mole, and more preferably 20 to 85% by mole.

Examples of the monomer (a1) having an acid labile (2) group and a carbon-carbon double bond include a monomer represented by the formula (a1-4). These monomers may be referred to as "monomer (a1-4)" hereinafter.

Wherein R ^a32 represents a hydrogen atom, a halogen atom or a C ₁ to C ₆ alkyl group optionally having a halogen atom; and R ^a33 independently represents a halogen atom, a hydroxyl group, a C ₁ to C ₆ alkyl group, C ₁ at each occurrence. To a C ₆ alkoxy group, a C ₂ to C ₄ fluorenyl group, a C ₂ to C ₄ methoxy group, an acryl fluorenyl group or a methacryl fluorenyl group; 1a represents an integer of 0 to 4; and R ^a34 and R ^a35 independently represent hydrogen. An atom or a C ₁ to C ₁₂ hydrocarbon group; X ^a2 represents a single bond or an optionally substituted C ₁ to C ₁₇ divalent aliphatic hydrocarbon group, wherein the hydrogen atom contained therein may be via a halogen atom, a hydroxyl group, a C ₁ to C ₆ alkyl group. a C ₁ to C ₆ alkoxy group, a C ₂ to C ₄ fluorenyl group, and a C ₂ to C ₄ decyloxy group, and one or more of the -CH ₂ - contained therein may be via -CO-, -O- , -S-, -SO ₂ - or -N(R ^c )-substitution, R ^c represents a hydrogen atom or a C ₁ to C ₆ alkyl group: Y ^a3 represents a C ₁ to C ₁₈ hydrocarbon group, wherein the hydrogen atom contained therein may Substituted by a halogen atom, a hydroxyl group, a C ₁ to C ₆ alkyl group, a C ₁ to C ₆ alkoxy group, a C ₂ to C ₄ fluorenyl group, and a C ₂ to C ₄ methoxy group.

Examples of the alkyl group having a halogen atom as required in R ^a32 include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluoro second butyl group, and a perfluoro group. Tributyl, perfluoropentyl, perfluorohexyl, trichloromethyl, tribromomethyl and triiodomethyl.

Examples of alkyl groups, alkoxy groups, and the like include the same as the above examples.

Examples of sulfhydryl groups include ethyl acetyl, propyl thiol and butyl sulfhydryl.

Examples of the decyloxy group include an ethoxylated group, a propyloxy group, and a butoxy group.

In the formula (a1-4), the alkyl group of R ^a32 and R ^a33 is preferably a C ₁ to C ₄ alkyl group, more preferably a C ₁ to C ₂ alkyl group, and still more preferably a methyl group.

The alkoxy group of R ^a33 is preferably a C ₁ to C ₄ alkoxy group, more preferably a C ₁ to C ₂ alkoxy group, and still more preferably a methoxy group.

Examples of the hydrocarbon group of R ^a34 and R ^a35 include any of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.

Preferred examples of the aliphatic group include isopropyl, n-butyl, t-butyl, t-butyl, pentyl, hexyl, octyl and 2-ethylhexyl groups.

Preferable examples of the alicyclic hydrocarbon group include a monocyclic or polycyclic saturated hydrocarbon group such as cyclohexyl, adamantyl, 2-alkyl-adamantan-2-yl, 1-(1-adamantan-1-yl)-1 - alkyl, paraffin-1-yl and isodecyl.

Preferable examples of the aromatic hydrocarbon group include phenyl, naphthyl, anthranil, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl , xylyl, cumyl, 2,4,6-trimethylphenyl, biphenyl, anthracenyl, phenanthryl, 2,6-diethylphenyl, and 2-methyl-6-ethylbenzene base.

The hydrocarbon group of Y ^a3 is preferably a C ₁ to C ₁₈ aliphatic hydrocarbon group, a C ₃ to C ₁₈ alicyclic hydrocarbon group, and a C ₆ to C ₁₈ aromatic hydrocarbon group.

Preferred examples of the substituent which may be optionally substituted in X ^a2 and Y ^a3 include a hydroxyl group.

Examples of the monomer represented by the formula (a1-4) include the following monomers.

When the resin (AA) contains a structural unit derived from a monomer represented by the formula (a1-4), the ratio is usually 10 to 95 mol%, preferably 15 based on the total structural unit constituting the resin (AA). Up to 90% by mole, more preferably 20 to 85% by mole.

Examples of the monomer having an acid labile group (2) and a carbon-carbon double bond include a monomer represented by the formula (a1-5). These monomers may be referred to as "monomer (a1-5)" hereinafter.

Wherein R ³¹ represents a hydrogen atom, a halogen atom or a C ₁ to C ₆ alkyl group optionally having a halogen atom; and L ¹ to L ³ independently represent *-O-, *-S- or *-O-(CH _{2 K1} -CO-O-, k1 represents an integer 1 to 7, * represents a bond bonded to a carbonyl group (-CO-); s1 represents an integer 1 to 4; s1' represents an integer 0 to 4; Z ¹ represents a single bond or The C ₁ to C ₆ alkanediyl group, and the -CH ₂ - contained in the alkanediyl group may be replaced by -O- or -CO-.

In the formula (a1-5), R ^{31 is} preferably a hydrogen atom, a methyl group or a trifluoromethyl group; L ^{1 is} preferably -O-; and L ² and L ^{3 are} preferably independently *-O- or *-S. And, more preferably, one of them is -O- and the other is -S-; s1 is preferably 1; s1' is preferably an integer of 0 to 2; Z ^{1 is} preferably a single bond or -CH ₂ - CO-O-.

Examples of the compound represented by the formula (a1-5) include the following compounds.

When the resin (AA) contains a structural unit derived from a monomer represented by the formula (a1-5), the ratio of the total structural unit constituting the resin (AA) is usually 10 to 95 mol%, preferably 15 Up to 90% by mole, and more preferably 20 to 85% by mole.

Further, the monomer (a1) having an acid labile group (1) and a carbon-carbon double bond can be used for the resin (AA).

Specific examples of such other monomers include the following monomers.

When the resin (AA) contains structural units derived from other acid labile monomers, the total proportion of the constituent units constituting the resin (AA) is usually from 10 to 95 mol%, preferably from 15 to 90 mol. % ear, and more preferably 20 to 85 mole%.

<acid stable monomer>

The resin (AA) is preferably a copolymer of the compound (a), a monomer having an acid labile group (a1), and a monomer having no acid labile group (hereinafter may be referred to as "acid-stable monomer").

The resin (AB) is preferably a copolymer of the compound (a) and an acid-stable monomer.

The acid-stable monomer may be used as a single compound or as a mixture of two or more compounds.

When the resin (AA) is produced as an acid-stable monomer, the ratio of the acid-stable monomer can be adjusted according to the amount of the acid-labile monomer (a1). For example, the ratio of [acid-labile monomer (a1)]: [acid-stable monomer] is preferably from 10 to 80 mol%: from 90 to 20 mol%, and more preferably from 20 to 60 mol%: 80 Up to 40% by mole.

When a monomer having an adamantyl group is used as the monomer (a1), the ratio of the monomer having an adamantyl group (in particular, having an acid labile group) based on the monomer having an acid labile group (a1) The monomer of (a1-1) is preferably 15 mol% or more. When the molar ratio of the monomer having an adamantyl group is increased within this range, the dry etching deviation of the resulting resist is improved. When the ratio of the acid labile monomer and the acid stabilizing monomer is maximized, the compound (a) can be used as the acid stable monomer.

As the acid-stable monomer, a monomer having a hydroxyl group or a lactone ring is preferred. When a structural unit containing a structural unit derived from an acid-stable monomer having a hydroxyl group (hereinafter, such an acid-stable monomer may be referred to as "acid-stable monomer (a2)") or an acid-stable monomer having a lactone ring (hereinafter, When such an acid-stable monomer is referred to as a "acid-stable monomer (a3)") resin, there is a tendency to improve the adhesion of the resist to the substrate and the resolution of the resist.

<Acid Stabilized Monomer (a2)>

The acid-stable monomer (a2) is preferably selected depending on the kind of the exposure light source when the resist pattern is produced.

That is, when KrF is excited by laser lithography (248 nm), or high energy irradiation such as electron beam or EUV light is used for the resist composition, it is preferred to use an acid-stable monomer having a phenolic hydroxyl group (a2-0). For example, hydroxystyrenes are used as the acid-stable monomer (a2) having a hydroxyl group. When using ArF to excite laser lithography (193 nm), that is, short-wavelength excitation of laser lithography, it is preferred to use an acid-stable monomer (a2) having a hydroxyadamantyl group represented by the formula (a2-1) as having The acid of the hydroxyl group stabilizes the monomer (a2). The acid-stable monomer (a2) having a hydroxyl group may be used as a single compound or a mixture of two or more compounds.

An example of the acid-stable monomer (a2) having a phenolic hydroxyl group, including a styrene monomer represented by the formula (a2-0) (hereinafter, the monomer may be referred to as "acid-stable monomer (a2-0)") such as P- or m-hydroxystyrene.

Wherein R ^a30 represents a hydrogen atom, a halogen atom or a C ₁ to C ₆ alkyl group optionally having a halogen atom; and R ^a31 independently represents a halogen atom, a hydroxyl group, a C ₁ to C ₆ alkyl group, C ₁ at each occurrence. To C ₆ alkoxy, C ₂ to C ₄ fluorenyl, C ₂ to C ₄ decyloxy, propylene fluorenyl or methacryl fluorenyl: ma represents an integer of 0 to 4.

In the formula (a2-0), ^examples of the alkyl group having a halogen atom of R ^{a30 include the} same examples as R ^a32 in the above formula (a1-4).

The alkyl group of R ^a30 and R ^a31 is preferably a C ₁ to C ₄ alkyl group, more preferably a C ₁ to C ₂ alkyl group, and still more preferably a methyl group.

The alkoxy group of R ^a31 is preferably a C ₁ to C ₄ alkoxy group, more preferably a C ₁ to C ₂ alkoxy group, and still more preferably a methoxy group.

Ma is preferably 0, 1 or 2, more preferably 0 or 1, and still more preferably 0.

When the resin (A) is produced using the acid-stable monomer (a2-0), a monomer which protects the phenolic hydroxyl group with a protecting group can be used. These protecting groups may be groups which are deprotected by contact with an acid or a base. Since the phenolic hydroxyl group protected by the protecting group is deprotected by contact with an acid or a base, the acid stabilizing monomer (a2-0) can be easily obtained. However, since the resin (AA) has a structural unit derived from a monomer having the acid labile group (a1) as described above, when the phenolic hydroxyl group protected by the protecting group is deprotected, it is preferred to The phenolic hydroxyl group is placed in contact with the base, so that the acid labile group is not seriously damaged. Examples of protecting groups that can be deprotected by a base include ethenyl. Examples of the base include 4-dimethylaminopyrizine and triethylamine.

Specific examples of the acid-stable monomer (a2-0) include the following monomers.

Among these, 4-hydroxystyrene and 4-hydroxy-α-methylstyrene are preferred. These 4-hydroxystyrenes and 4-hydroxy-α-methylstyrene can protect their phenolic hydroxyl groups with a suitable protecting group.

When the resin (AA) contains a structural unit derived from a monomer represented by the formula (a2-0), the ratio is usually from 5 to 95 mol%, preferably 10, based on the entire structural unit constituting the resin (AA). Up to 80% by mole, and more preferably 15 to 80% by mole.

When the resin (AB) contains a structural unit derived from a monomer represented by the formula (a2-0), the ratio is usually from 5 to 95 mol%, preferably 10, based on the entire structural unit constituting the resin (AB). Up to 80% by mole, and more preferably 15 to 80 moles.

Examples of the acid-stable monomer having a hydroxyadamantyl group include a monomer represented by the formula (a2-1) (hereinafter, the monomer may be referred to as "acid-stable monomer (a2-1)").

Wherein, L ^a3 represents *-O- or *-O-(CH ₂ ) _k2 -CO-O-, k2 represents an integer of 1 to 7, * represents a bond bonded to a carbonyl group (-CO-); and R ^a14 represents hydrogen Atom or methyl; R ^a15 and R ^a16 independently represent a hydrogen atom, a methyl group or a hydroxyl group; o1 represents an integer of 0 to 10.

In the formula (a2-1), L ^{a3 is} preferably *-O-, *-O-(CH ₂ ) _k2' -CO-O-, where k2' represents an integer of 1 to 4, and preferably *-O-; R ^{a14 is} preferably a methyl group.

R ^{a15 is} preferably a hydrogen atom.

R ^{a16 is} preferably a hydrogen atom or a hydroxyl group.

O1 is preferably an integer of 0 to 3, and more preferably an integer of 0 or 1.

Examples of the acid-stable monomer (a2-1) having a hydroxyadamantyl group include the following monomers. Among these, 3-hydroxyadamantan-1-yl (meth)acrylate, 3,5-dihydroxyadamantan-1-yl (meth)acrylate, and methyl (meth)acrylate 1- (3,5-Dihydroxyadamantan-1-yloxycarbonyl) ester, and 3-hydroxyadamantan-1-yl (meth)acrylate and 3,5-dihydroxy(meth)acrylate Adamantyl-1-yl ester is preferred, and 3-hydroxyadamantan-1-yl (meth)acrylate and 3,5-dihydroxyadamantan-1-yl methacrylate are more preferred.

When the resin (AA) contains a structural unit derived from a monomer represented by the formula (a2-1), the ratio is usually from 3 to 45 mol%, preferably 5, based on the entire structural unit constituting the resin (AA). Up to 40% by mole, and more preferably 5 to 35% by mole.

When the resin (AB) contains a structural unit derived from a monomer represented by the formula (a2-1), the ratio is usually from 3 to 45 mol%, preferably 5, based on the entire structural unit constituting the resin (AB). Up to 40% by mole, and more preferably 5 to 35% by mole.

<acid-stable monomer (a3)>

The lactone ring contained in the acid-stable monomer (a3) may be a monocyclic compound such as a β-propiolactone ring, a γ-butyrolactone, a δ-valerolactone or a condensation of a monocyclic lactone ring with other rings. ring. Among these, a condensed ring of γ-butyrolactone and γ-butyrolactone and another ring is preferred.

An example of the acid-stable monomer (a3) having a lactone ring includes a monomer represented by any one of the formula (a3-1), the formula (a3-2) or the formula (a3-3). This monomer may be used as a single compound or as a mixture of two or more compounds.

Wherein, L ^a4 to L ^a6 independently represent *-O- or *-O-(CH ₂ ) _k3 -CO-O-, k3 represents an integer of 1 to 7, and * represents a bond bonded to a carbonyl group; R ^a18 to R ^A20 independently represents a hydrogen atom or a methyl group; R ^a21 represents a C ₁ to C ₄ alkyl group; R ^a22 and R ^a23 independently represent a carboxyl group, a cyano group or a C ₁ to C ₄ alkyl group; p1 represents an integer of 0 to 5; q1 And r1 independently represents integers 0 to 3.

In the formulae (a3-1) to (a3-3), L ^a4 to L ^{a6 are} preferably independently *-O-, *-O-(CH ₂ ) _k3' -CO-O-, here, k3 'Expresss an integer 1 to 4, and more preferably *-O-.

R ^a18 to R ^{a20 are} preferably a methyl group.

R ^{a21 is} preferably a methyl group.

R ^a22 and R ^a23 are preferably a carboxyl group, a cyano group or a methyl group.

P1, q1 and r1 are preferably independently an integer of 0 to 2, and more preferably 0 or 1.

An example of an acid-stable monomer (a3-1) having a γ-butyrolactone ring includes the following monomers.

Examples of the acid-stable monomer (a3-2) having a γ-butyrolactone ring and a norbornene ring represented by the formula include the following monomers.

An example of the acid-stable monomer (a3-3) having a condensed ring of a γ-butyrolactone ring and a cyclohexane ring represented by the formula includes the following monomers.

Among the acid-stable monomers having a lactone ring (a3), (meth)acrylic acid (5-o-oxy-4-oxatricyclo[4.2.1.0 ^3,7 ]decane- is preferred. 2-yl)ester, tetrahydro-2-oxo-3-furyl (meth)acrylate and 2-(5-o-oxy-4-oxatricyclo[4-. ^3,7 ]decane-2-yloxy)-2-oxoethyl ester, and more preferably a (meth) acrylate compound.

When the resin (AA) contains a structural unit derived from a monomer represented by the formula (a3-1), a structural unit derived from the monomer represented by the formula (a3-2) and/or derived from the formula (a3-3) The structural unit of the monomer is usually 5 to 50 mol%, preferably 10 to 40 mol%, and more preferably 15 to 40 mol, based on the total structural unit constituting the resin (AA). ear%.

When the resin (AA) contains a structural unit derived from the acid-stable monomer (a3) having a lactone ring, the total proportion of the structural unit constituting the resin (AA) is preferably from 5 to 60 mol%. And more preferably 15 to 55 mol%.

When the resin (AB) contains a structural unit derived from the acid-stable monomer represented by the formula (a3-1), a structural unit derived from the monomer represented by the formula (a3-2), and/or derived from the formula (a3-3) The structural unit of the monomer shown is usually 5 to 50 mol%, preferably 10 to 40 mol%, and more preferably 15 to 40, based on the total structural unit constituting the resin (AB). Moer%.

When the resin (AB) contains a structural unit derived from the acid-stable monomer (a3) having a lactone ring, the total proportion of the structural unit constituting the resin (AB) is preferably from 5 to 60 mol%. And more preferably 15 to 55 mol%.

<acid-stable monomer (a4)>

The acid-stable monomer (a4) and the acid-stable monomer (a5) can be used to produce a resin (AA).

The acid-stable monomer (a4) has a group represented by the following formula (3).

Wherein R ¹⁰ represents a C ₁ to C ₆ fluorinated alkyl group.

Examples of the fluorine-containing alkyl group in R ¹⁰ include difluoromethyl, trifluoromethyl, 1,1-difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, Perfluoroethyl, 1,1,2,2-tetrafluoropropyl, 1,1,2,2,3,3-hexafluoropropyl, perfluoroethylmethyl, 1-(trifluoromethyl) -1,2,2,2-tetra(trifluoroethyl), perfluoropropyl, 1,1,2,2-tetrafluorobutyl, 1,1,2,2,3,3-hexafluorobutyl 1,1,2,2,3,3,4,4-octafluorobutyl, perfluorobutyl, 1,1-bis(trifluoro)methyl-2,2,2-trifluoroethyl , 2-(perfluoropropyl)ethyl, 1,1,2,2,3,3,4,4-octafluoropentyl, perfluoropentyl, 1,1,2,2,3,3, 4,4,5,5-decafluoropentyl, 1,1-bis(trifluoromethyl)-2,2,3,3,3-pentafluoropropyl, 2-(perfluorobutyl)ethyl 1,1,2,2,3,3,4,4,5,5-decafluorohexyl, 1,1,2,2,3,3,4,4,5,5,6,6-ten Difluorohexyl, perfluoropentylmethyl and perfluorohexyl.

The fluorine-containing alkyl group of R ¹⁰ preferably has 1 to 4 carbon atoms, preferably a trifluoromethyl group, a perfluoroethyl group, and a perfluoropropyl group, and more preferably a trifluoromethyl group.

Specific examples of the acid-stable monomer (a4) having a group represented by the formula (a4) include the following monomers.

When the resin (AA) contains a structural unit derived from an acid-stable monomer represented by the formula (a4), the ratio is usually from 1 to 30 mol based on the total structural unit (100 mol%) of the resin (AA). %, preferably from 3 to 25 mol%, and more preferably from 5 to 20 mol%.

When the resin (AB) contains a structural unit derived from an acid-stable monomer represented by the formula (a4), the ratio is usually from 5 to 90 mol based on the total structural unit (100 mol%) of the resin (AB). %, preferably 10 to 80 mol%, and more preferably 20 to 70 mol%.

<acid-stable monomer (a5)>

The acid-stable monomer (a5) has a group represented by the formula (4).

Wherein R ¹¹ represents a C ₆ to C ₁₂ aromatic hydrocarbon group optionally substituted; R ¹² represents a C ₁ to C ₁₂ hydrocarbon group optionally substituted, and the hydrocarbon group may contain a hetero atom; A ² represents a single bond, -(CH ₂ ) _M10 -SO ₂ -O-* or -(CH ₂ ) _m10 -CO-O-*, F-(CH ₂ ) _m10 -] -CH ₂ - may be via -O-, -CO- or -SO ₂ - Substitution, the hydrogen atom contained in [-(CH ₂ ) _m10 -] may be replaced by a fluorine atom; m10 represents an integer of 1 to 12.

Examples of the aromatic hydrocarbon group of R ¹¹ include an aromatic group such as a phenyl group, a naphthyl group, a p-methylphenyl group, a p-tert-butylphenyl group, a p-adamantylphenyl group, a tolyl group, a xylyl group, Phenylphenyl, 2,4,6-trimethylphenyl, biphenyl, anthracenyl, phenanthryl, 2,6-diethylphenyl, and 2-methyl-6-ethylphenyl.

The hydrogen atom contained in the aromatic hydrocarbon group may be replaced by a C ₁ to C ₄ alkyl group, a halogen atom, a phenyl group, a nitro group, a cyano group, a hydroxyl group, a phenoxy group, and a third butyl group.

Specific examples of the preferred group of R ¹¹ include the following groups. * indicates a bond to a carbon atom.

The hydrocarbon group of R ¹² may be any of a linear aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.

Typical examples of the aliphatic hydrocarbon group are an alkyl group, and examples of the alkyl group include the same groups as described above.

Examples of the alicyclic hydrocarbon group include the same examples as described above.

When R ¹² is an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, these may include a hetero atom. Examples of the hetero atom include a halogen atom, a sulfur atom, an oxygen atom, and a nitrogen atom, and may include a type of a bonding group such as a sulfonyl group and a carbonyl group.

Specific examples of R ¹² containing a hetero atom include the following groups.

When R ¹² is an aromatic hydrocarbon group, specific examples thereof include the same examples as R ¹¹ .

Specific examples of A ² include the following groups.

The acid-stable monomer (a5) containing a group represented by the formula (4) includes an acid-stable monomer represented by the formula (a5-1).

Wherein R ¹³ represents a hydrogen atom or a methyl group: R ¹¹ , R ¹² and A ^{2 are} as defined above.

Specific examples of the acid-stable monomer (a5-1) include the following monomers.

When the resin (AA) contains a structural unit derived from a monomer represented by the formula (a5-1), the ratio is usually from 1 to 30 mol%, preferably 3, based on the entire structural unit constituting the resin (AA). Up to 25 mol%, and more preferably 5 to 20 mol%.

When the resin (AB) contains a structural unit derived from a monomer represented by the formula (a5-1), the ratio is usually from 5 to 90 mol, based on the total structural unit (100 mol%) constituting the resin (AB). %, preferably 10 to 80 mol%, and more preferably 20 to 70 mol%.

<acid-stable monomer (a6)>

The acid-stable monomer (a6) is a monomer represented by the formula (a6-1).

Wherein ring W ¹ represents a C ₃ to C ₃₆ alicyclic hydrocarbon group; A ³ represents a single bond or a C ₁ to C ₁₇ divalent aliphatic hydrocarbon group, and -CH ₂ - contained in the aliphatic hydrocarbon group may be -O- or - CO-substitution, however, the atom bonded to -O- is a carbon atom; R ¹⁴ represents a C ₁ to C ₆ alkyl group having a halogen atom, a hydrogen atom or a halogen atom; R ¹⁵ and R ¹⁶ independently represent A C ₁ to C ₆ alkyl group having a halogen atom is required.

The alicyclic hydrocarbon group of the ring W ¹ includes a monocyclic or polycyclic hydrocarbon group, preferably a C ₅ to C ₁₈ alicyclic hydrocarbon group, and more preferably a C ₆ to C ₁₂ alicyclic hydrocarbon group. Examples thereof include a ring represented by the formula (KA-1) to the formula (KA-19). That is, the following bases in the formula (a6-1),

One of the hydrogen atoms bonded to any of the atoms constituting the ring of the formula (KA-1) to the formula (KA-19), replaced by a bond bonded to A ³ , and the other two bonds to form a ring The hydrogen atoms of the other atoms are bonded to -O-CO-R ¹⁵ and the group bonded to -O-CO-R ¹⁶ , respectively.

Examples of the ring W ¹ preferably include a cyclohexane ring, an adamantane ring, a norbornene ring, and a norbornane ring.

Examples of the divalent aliphatic hydrocarbon group of A ³ include: a linear alkanediyl group such as a methylene group, an ethylidene group, a propane-1,3-diyl group, a propane-1,2-diyl group, butane-1, 4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, decane-1, 9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, fourteen Alkane-1,14-diyl, pentadecane-1,15-diyl, hexadecane-1,16-diyl, heptadecane-1,17-diyl, ethane-1,1-di a base, a propane-1,1-diyl group and a propane-2,2-diyl group; a branched alkanediyl group such as wherein a linear alkanediyl group is bonded to a C ₁ to C ₄ alkyl group (such as methyl, ethyl, or propyl a side chain of a base group, an isopropyl group, a butyl group, a second butyl group, and a third butyl group, such as butane-1,3-diyl, 2-methylpropane-1,3-diyl, 2 -methylpropane-1,2-diyl, pentane-1,4-diyl, 2-methylbutane-1,4-diyl; mono-alicyclic hydrocarbon group such as cyclobutane-1,3- Diyl, cyclopentane-1,3-diyl, cyclohexane-1,2-diyl, 1-methylhexane-1,2-diyl, cyclohexane-1,4-diyl, Cyclooctane-1,2-diyl, cyclooctane-1,5-diyl; poly- Alicyclic hydrocarbon groups such as norbornane-2,3-diyl, norbornane-1,4-diyl, norbornane-2,5-diyl, adamantane-1,5-diyl and adamantane- 2,6-diyl; and a combination of two or more bases.

The aliphatic hydrocarbon group of A ³ may have a substituent.

Examples of the combination of the alkanediyl group and the alicyclic hydrocarbon group include the following groups.

Wherein X ^X1 and X ^X2 independently represent a C ₁ to C ₆ alkanediyl group or a single bond, but each of them, X ^X1 and X ^X2 are not a single bond, and the total number of carbon atoms of the group is 17 or 17 the following.

Examples of the -CH ₂ - contained in the aliphatic hydrocarbon group in A ³ are replaced by -O- or -CO-, and include, for example, the same examples as the (a-g1) group in the formula (a).

A ^{3 is} preferably a single bond or a group of the formula *-(CH ₂ ) _s1 -CO-O-, s1 represents an integer of 1 to 6, * represents a bond, and more preferably a single bond or *-CH ₂ -CO -O-.

R ^{14 is} preferably a hydrogen atom or a methyl group.

The halogen atom of R ¹⁴ to R ¹⁶ is preferably a fluorine atom.

Examples of the alkyl group having a halogen atom include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluoro-second butyl group, a perfluoro-t-butyl group, and a whole. Fluoropyl and perfluorohexyl. Among these, a trifluoromethyl group, a perfluoroethyl group, and a perfluoropropyl group are preferred.

Examples of the acid-stable monomer (a6-1) include the following acid-stable monomers. R ¹⁴ to R ¹⁶ and A ³ are the same as defined above.

Among these, an acid-stable monomer represented by the following formula is preferred.

Specific examples of the acid-stable monomer (a6-1) include the following acid-stable monomers.

A preferred acid-stable monomer (a6-1) can be produced by reacting a compound of the formula (a6-1-a) with a compound of the formula (a6-1-b).

Wherein R ¹⁴ , R ¹⁵ , R ¹⁶ , A ³ and W ¹ have the same definitions as described above.

A typical compound represented by the formula (a6-1-a) is 1-methylpropenyloxy-4-oxo-adamantane described in JP2002-226436-A.

Examples of the compound represented by the formula (a6-1-b) include pentafluoropropionic anhydride, heptafluorobutyric anhydride, and trifluorobutyric anhydride. This reaction is preferably carried out in the vicinity of the boiling point of the compound represented by the formula (a6-1-b) used.

When the resin (AA) contains a structural unit derived from a monomer represented by the formula (a6), the ratio is usually from 1 to 30 mol%, preferably from 3 to 25, based on the entire structural unit constituting the resin (AA). Mole%, and more preferably 5 to 20 mol%.

When the resin (AB) contains a structural unit derived from a monomer represented by the formula (a6), the ratio is usually from 5 to 90 mol%, preferably from 10 to 80, based on the entire structural unit constituting the resin (AB). Mole%, and more preferably 20 to 70 mol%.

<Acid Stabilized Monomer (a7)>

Examples of the acid-stable monomer other than the above include, for example, maleic anhydride represented by the formula (a7-1), itaconic anhydride represented by the formula (a7-2) or a norbornene ring represented by the formula (a7-3). Acid stable monomer.

Wherein, R ^a25 and R ^a26 independently represent a hydrogen atom, the hydroxyl group optionally having a C ₁ to C ₃ alkyl group, a cyano group, a carboxyl group or a -COOR ^a27, or R ^a25 and R ^a26 may be bonded to each other to form -CO- O-CO-, R ^a27 represents a C ₁ to C ₁₈ aliphatic hydrocarbon group, and one or more -CH ₂ - contained in the aliphatic hydrocarbon group may be replaced by -O- or -CO-, but wherein -COOR ^a27 is excluded The group of the acid labile group, that is, R ^a27 does not include a group in which the tertiary carbon atom is bonded to -O-.

Examples of the alkyl group having a hydroxyl group as required for R ^a25 and R ^a26 include, for example, a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a 2-hydroxyethyl group.

The aliphatic hydrocarbon group in R ^a27 has a C ₁ to C ₈ alkyl group and a C ₄ to C ₁₈ alicyclic hydrocarbon group, and more preferably a C ₁ to C ₆ alkyl group and a C ₄ to C ₁₂ alicyclic hydrocarbon group, and More preferably, it is a methyl group, an ethyl group, a propyl group, a 2-sided oxy-oxolane-3-yl group, and a 2-sided oxy-oxolane-4-yl group.

Specific examples of the acid-stable monomer having a norbornene ring (a7-3) include 2-northene, 2-hydroxy-5-norbornene, 5-northene-2-carboxylic acid, 5-norbornium Methyl 2-carboxylate, 2-hydroxy-1-ene-2-carboxylic acid 2-hydroxy-1-ethyl ester, 5-northene-2-methanol, and 5-northene-2,3-dicarboxylate Anhydride.

When the resin (AA) contains a structural unit derived from a monomer represented by the formula (a7-1), the monomer and/or formula represented by the formula (a7-2) is represented by all the structural units constituting the resin (AA). The total proportion of the monomers shown in a7-3) is usually from 2 to 40 mol%, preferably from 3 to 30 mol%, and more preferably from 5 to 20 mol%.

When the resin (AB) contains a structural unit derived from a monomer represented by the formula (a7-1), a monomer represented by the formula (a7-2), and/or a monomer represented by the formula (a7-3), The total proportion of all structural units of (AB) is usually from 5 to 70 mol%, preferably from 10 to 60 mol%, and more preferably from 20 to 50 mol%.

Further, examples of the acid-stable monomer other than the above include a monomer having a sultone ring represented by the formula (a7-4).

Wherein, L ^a7 represents an oxygen atom or *-T-(CH ₂ ) _k2 -CO-O-, k2 represents an integer of 1 to 7, T represents an oxygen atom or NH, * represents a single bond bonded to a carbonyl group; R ^a28 represents A hydrogen atom or a methyl group; W ¹⁰ represents a group having a sultone ring which is optionally substituted.

The sultone ring is a ring in which two adjacent methylene groups are respectively substituted with an oxygen atom and a sulfonyl group, and examples thereof include the following ring. The sultone ring group is one in which a hydrogen atom contained in the following sultone ring is replaced by a bond corresponding to a bond bonded to L ^{a7 in} the formula (a7-4).

a group having a sultone ring optionally substituted, meaning that a hydrogen atom other than a hydrogen atom which has been replaced by a bond contained in a sultone ring is substituted with a substituent (a valence group other than a hydrogen atom), And examples thereof include a hydroxyl group, a cyano group, a C ₁ to C ₆ alkyl group, a C ₁ to C ₆ fluorine-containing alkyl group, a C ₁ to C ₆ hydroxyalkyl group, a C ₁ to C ₆ alkoxy group, and C ₁ to C ₇ Alkoxycarbonyl, C ₁ to C ₇ fluorenyl and C ₁ to C ₈ decyloxy.

Specific examples of the acid-stable monomer (a7-4) having a sultone ring include the following monomers.

When the resin (AA) contains a structural unit derived from the acid-stable monomer (a7) represented by the formula (a7-4), the proportion of the total structural unit (100 mol%) constituting the resin (AA) is usually 2 to 40 mol%, preferably 3 to 35 mol%, and more preferably 5 to 30 mol%.

When the resin (AB) contains a structural unit derived from the acid-stable monomer (a7) represented by the formula (a7-4), the ratio is usually from 5 to 90 mol% based on the entire structural unit constituting the resin (AB). It is preferably from 10 to 80 mol%, and more preferably from 20 to 70 mol%.

<acid-stable monomer (a8)>

The following acid-stabilizing monomer (a8) containing a fluorine atom is used for the production of the resin (A).

Among these, 5-(3,3,3-trifluoro-2-hydroxy-2-[trifluoromethyl]propyl) (meth)acrylate having a mono- or poly-alicyclic hydrocarbon group is preferred. Bicyclo[2.2.1]hept-2-yl ester, 6-(3,3,3-trifluoro-2-hydroxy-2-[trifluoromethyl]propyl)bicyclo(2)[2.2.1 Hept-2-yl ester, 4,4-bis(trifluoromethyl)-3-oxatricyclo[4.2.1.0 ^2,5 ]decyl.

When the resin (AA) contains a structural unit derived from a monomer represented by the formula (a8), the ratio is usually from 1 to 20 mol%, preferably from 2 to 15 based on the total structural unit constituting the resin (AA). Mole%, and more preferably 3 to 10 mol%.

When the resin (AB) contains a structural unit derived from a monomer represented by the formula (a8), the ratio is usually from 5 to 90 mol%, based on the total structural unit (100 mol%) constituting the resin (AB). It is preferably from 10 to 80 mol%, and more preferably from 20 to 70 mol%.

<Manufacture of resin>

The resin (AA) may be a copolymer in which at least a compound (a) and a monomer (a1), and if necessary, an acid-stable monomer are polymerized, and preferably a compound (a), a monomer (a1), and an acid are polymerized. A copolymer of a monomer (a2) and/or an acid-stable monomer (a3) is stabilized.

In the production of the resin (AA), the monomer (a1) to be used is preferably at least one of a monomer having an adamantyl group (a1-1) and a monomer having a cycloalkyl group (a1-2), and More preferably, it is a monomer (a1-1) which has an adamantyl group.

The acid-stable monomer is preferably a monomer having a hydroxyadamantyl group (a2-1) and an acid-stable monomer (a3). The monomer (a3) having a lactone ring is preferably a monomer having a γ-butyrolactone ring (a3-1) and a monomer having a condensed ring of a γ-butyrolactone ring and a norbornene ring (a3- 2) At least one of them.

The resin (AA) can be produced by a known polymerization method, for example, a radical polymerization method. The monomer may be used as a single compound or as a mixture of two or more compounds.

When the resin (AA) contains a structural unit derived from the monomer (a1), the total proportion of the structural unit (100 mol%) of the resin (AA) is usually 10 to 95 mol%, preferably 20 to 80% by mole.

The weight average molecular weight of the resin (AA) is preferably 2,500 or more (more preferably 3,000 or more, and still more preferably 3,500 or more), and 50,000 or less (more preferably 30,000 or less, and still more preferably 10,000 or less). The weight average molecular weight is determined by gel permeation chromatography using polystyrene as a standard product. The detailed conditions of this analysis are described in the examples.

The resin (AB) may be an acid-stable resin having only a structural unit derived from the compound (a), or a structural unit derived from the compound (a) and derived from an acid-stable monomer (preferably at least one acid-stable single) The body is selected from the acid-stable resins of the structural units of the acid-stable monomers (a2) to (a8). Among these, the preferred acid-stable resin is a structural unit derived from the compound (a), and a structural unit derived from the acid-stable monomer (a5) and a structural unit derived from the acid-stable monomer (a6). One.

The resist composition of the present invention may contain a resin (AB) in addition to the resin (AA) or a resin (AB) in place of the resin (AA). When the resin (AB) is added in addition to the resin (AA), the content of the resin (AB) is usually 0.1 to 20 parts by weight based on 100 parts by weight of the resin (AA).

The resin (AB) can be produced by a known polymerization method, for example, a radical polymerization method. When the resin (AB) is produced, the monomer may be used as a single compound or as a mixture of two or more compounds.

The weight average molecular weight of the resin (AB) is preferably 8000 or more (more preferably 10,000 or more, and still more preferably 11,000 or more), and 80,000 or less (more preferably 60,000 or less, and still more preferably 50,000 or less).

<Resin (X)>

When the resist composition of the present invention contains a resin (AB) in place of the resin (AA), the resist composition preferably further comprises a resin having a structural unit derived from a monomer having an acid labile group, that is, The resin having the above properties. These resins are not resins which are derived from the structural unit of the compound (a) but have the above properties. Hereinafter, these resins may be referred to as "resin (X)" as described below.

When the resist composition of the present invention contains the resin (X) in addition to the resin (AB), the content of the resin (AB) is, for example, 0.1 to 20 parts by weight based on 100 parts by weight of the resin (X).

The resin (X) can be used in combination with the resin (AA).

When the resist composition of the present invention contains the resin (AA) and the resin (X), the weight ratio of the resin (AA): (X) may be 1:100 to 99.9:0.1.

The resin (X) is preferably a copolymer in which at least a monomer (a1) and an acid-stable monomer (a2) and/or an acid-stable monomer (a3) are polymerized.

In the production of the resin (X), the monomer (a1) to be used is preferably at least one of the monomer (a1-1) having the adamantyl group and the monomer (a1-2) having the cycloalkyl group. And more preferably a monomer having an adamantyl group (a1-1).

The acid-stable monomer (a2) is preferably a monomer (a2-1) having the hydroxyadamantyl group, and the acid-stable monomer (a3) having a lactone ring preferably has a γ-butyrolactone ring. At least one of the monomer (a3-1) and the monomer (a3-2) having a condensed ring of a γ-butyrolactone ring and a norbornene ring.

The resin (X) can also be produced by a known polymerization method, for example, a radical polymerization method. The monomer may be a single compound or a mixture of two or more compounds.

When the resin (X) is produced, the ratio of the above monomers may be the same as the above, or may be any range in consideration of the properties of the resin. In particular, the monomer (a1) used: monomer (a2) and/or (a3) may have a molar ratio of from 10:90 to 95:5.

The weight average molecular weight of the resin (X) is preferably 2,500 or more (more preferably 3,000 or more, and still more preferably 3,500 or more), and 50,000 or less (more preferably 30,000 or less, and still more preferably 10,000 or less).

<acid generator (B)>

The acid generator (B) is classified into a nonionic or ionic acid generator. Two types of acid generators can be used as the resist composition of the present invention.

Examples of nonionic acid generators include organohalogen compounds: sulfonates such as 2-nitrobenzyl ester, aromatic sulfonate, oxime sulfonate, N-sulfonyloxy oxime N-sulfonyl oxyimide, sulfonyl oxyketone, and diazo naphthoquinone 4-sulfonate; terpenoids such as diterpenes, ketosulfone, and sputum Sulfone diazomethane.

Examples of ionic acid generators include sulfonium salts containing onium cations such as diazonium salts, phosphonium salts, sulfonium salts, and iodonium salts. .

Examples of the anion of the onium salt include a sulfonate anion, a sulfonylimide anion, and a sulfonylmethyde anion.

The acid generator (B) can be used for JP S63-26653-A, JP S55-164824-A, JP S62-69263-A, JP S63-146038-A, JP S63-163452-A, JP S62-153853. -A, JP S63-146029-A, US Pat. No. 3,779,778-B, US Pat. No. 3,849, 137-B, DE 3,914, 407-B, and EP-126, 712-A.

The fluorine-containing acid generator is preferably an acid generator (B), and more preferably a sulfonate represented by the formula (B1). Hereinafter, the acid generator may be referred to as an "acid generator (B1)". As described below. In the acid generator (B1), the positively charged Z ⁺ may be referred to as "organic cation" hereinafter, and the negatively charged person may be referred to as "sulfonic acid anion" by removing the organic cation from the compound.

Wherein Q ¹ and Q ² independently represent a fluorine atom or a C ₁ to C ₆ perfluoroalkyl group; L ^b1 represents an optionally substituted C ₁ to C ₁₇ divalent aliphatic hydrocarbon group, and -CH contained in the aliphatic hydrocarbon group ₂ - may be substituted by -O- or -CO-; Y represents a C ₁ to C ₁₈ aliphatic hydrocarbon group optionally substituted, and -CH ₂ - contained in the aliphatic hydrocarbon group may be -O-, -CO- or - SO ₂ -displacement; and Z ⁺ represents an organic cation.

Examples of the perfluoroalkyl group of Q ¹ and Q ² include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluoro second butyl group, and a perfluoro third group. Butyl, perfluoropentyl and perfluorohexyl.

Among these, Q ¹ and Q ^{2 are each} independently preferably a trifluoromethyl group or a fluorine atom, and more preferably all are fluorine atoms.

Examples of the divalent aliphatic hydrocarbon group of L ^b1 include a linear alkanediyl group such as methylene, ethyl, propane-1,3-diyl, propane-1,2-diyl, butane-1,4 -diyl,pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, decane-1,9 -diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane -1,14-diyl, pentadecane-1,15-diyl, hexadecane-1,16-diyl, heptadecane-1,17-diyl, ethane-1,1-diyl , propane-1,1-diyl and propane-2,2-diyl; branched alkanediyl such as wherein a linear alkanediyl group is bonded to a C ₁ to C ₄ alkyl group (such as methyl, ethyl, propyl a side chain of a base group, an isopropyl group, a butyl group, a second butyl group, and a third butyl group, such as butane-1,3-diyl, 2-methylpropane-1,3-diyl, 2 -methylpropane-1,2-diyl, pentane-1,4-diyl, 2-methylbutane-1,4-diyl; mono-alicyclic hydrocarbon group such as cyclobutane-1,3- Diyl, cyclopentane-1,3-diyl, cyclohexane-1,2-diyl, 1-methylhexane-1,2-diyl, cyclohexane-1,4-diyl, Cyclooctane-1,2-diyl, cyclooctane-1,5-diyl; poly- Cycloalkyl groups such as norbornane-2,3-diyl, norbornane-1,4-diyl, norbornane-2,5-diyl, adamantane-1,5-diyl and adamantane-2 , 6-diyl; and a combination of two or more bases.

Examples of the aliphatic hydrocarbon group of L ^b1 in which -CH ₂ - is substituted by -O- or -CO- contained in the aliphatic hydrocarbon group include, for example, a group represented by the formula (b1-1) to the formula (b1-6). Among these, a group represented by the formula (b1-1) to the formula (b1-4) is preferred, and a group represented by the formula (b1-1) or the formula (b1-2) is preferred.

In the formulae (b1-1) to (b1-6), the group is represented as corresponding to both sides of the formula (B1), that is, the left side of the group is bonded to C(Q ¹ )(Q ² ). - and the right side of the group is bonded to -Y (examples of formula (b1-1) to formula (b1-6) are the same as above). * indicates a bond.

Wherein, L ^b2 represents a single bond or a C ₁ to C ₁₅ divalent aliphatic hydrocarbon group, and the aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group: L ^b3 represents a single bond or a C ₁ to C ₁₂ divalent aliphatic hydrocarbon group, the fat The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group: L ^b4 represents a C ₁ to C ₁₃ divalent aliphatic hydrocarbon group, and the aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, and the total number of carbon atoms in L ^b3 and L ^b4 is at most 13 ; L ^b5 represents a C ₁ to C ₁₅ divalent saturated hydrocarbon group: L ^b6 and L ^b7 independently represent a C ₁ to C ₁₅ divalent aliphatic hydrocarbon group, and the aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group at L ^b6 and L ^The total number of carbon atoms in ^b7 is at most 16; L ^b8 represents a C ₁ to C ₁₄ divalent aliphatic hydrocarbon group, and the aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group: L ^b9 and L ^b10 independently represent C ₁ to C ₁₁ The valent aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, and the total number of carbon atoms in L ^b9 and L ^b10 is at most 12.

Among these, a divalent group represented by the formula (b1-1) is preferred, and a divalent group represented by the formula (b1-1) wherein L ^b2 represents a single bond or -CH ₂ - is preferred.

Specific examples of the divalent group represented by the formula (b1-1) include the following groups.

Specific examples of the divalent group represented by the formula (b1-2) include the following groups.

Specific examples of the divalent group represented by the formula (b1-3) include the following groups.

Specific examples of the divalent group represented by the formula (b1-4) include the following groups.

Specific examples of the divalent group represented by the formula (b1-5) include the following groups.

Specific examples of the divalent group represented by the formula (b1-6) include the following groups.

The aliphatic hydrocarbon group of L ^a1 may have a substituent.

Examples of the substituent thereof include a halogen atom, a hydroxyl group, a carboxyl group, a C ₆ to C ₁₈ aromatic hydrocarbon group, a C ₇ to C ₂₁ aralkyl group, a C ₂ to C ₄ fluorenyl group, and a glycidyloxy group.

Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a p-methylphenyl group, a p-tert-butylphenyl group, a p-adamantylphenyl group, a tolyl group, a xylyl group, a cumyl group, and 2, 4,6-Trimethylphenyl, biphenylyl, fluorenyl, phenanthryl, 2,6-diethylphenyl, and 2-methyl-6-ethylphenyl.

Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, and a naphthylethyl group.

Examples of sulfhydryl groups include ethyl acetyl, propyl thiol and butyl sulfhydryl.

The aliphatic hydrocarbon group of Y is preferably an alkyl group and an alicyclic hydrocarbon group or a combination thereof.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group, and a hexyl group. The alkyl group is preferably a C ₁ to C ₆ alkyl group.

Examples of the alicyclic hydrocarbon group include a group represented by the above formula (Y1) to formula (Y11). The alicyclic hydrocarbon group is preferably a C ₃ to C ₁₂ alicyclic hydrocarbon group.

Examples of Y in which -CH ₂ - contained in the aliphatic hydrocarbon group is replaced by -O-, -CO- or SO ₂ - include, for example, a cyclic ether group (one or two -CH ₂ - consists of one or two - O-substituted group), cyclic ketone group (one or two -CH ₂ - groups substituted by one or two -CO-), sultone ring group (the adjacent two -CH ₂ - as in a group substituted by -O- and -SO ₂ - or a lactone ring group as described in the formula (a7-4) (the adjacent two -CH ₂ - are replaced by -O- and -CO-, respectively) base).

Examples thereof include a group represented by the above formula (Y12) to formula (Y26).

Among these, the aliphatic hydrocarbon group of Y is preferably a group represented by the formula (Y1) to the formula (Y19), more preferably the following group.

Examples of the substituent of Y include a halogen atom (other than a fluorine atom), a hydroxyl group, a C ₁ to C ₁₂ alkoxy group, a C ₆ to C ₁₈ aromatic hydrocarbon group, a C ₇ to C ₂₁ aralkyl group, and a C ₂ to C group. _{A 4} -mercapto, epoxypropyloxy or -(CH ₂ ) _{j 2} -O-CO-R ^b1 group, wherein R ^b1 represents a C ₁ to C ₁₆ hydrocarbon group, and j 2 represents an integer of 0 to 4. The aromatic hydrocarbon group and the aralkyl group may further have a substituent such as a C ₁ to C ₆ alkyl group, a halogen atom or a hydroxyl group.

Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group, an octyloxy group, a 2-ethylhexyloxy group, a decyloxy group, a decyloxy group, and an undecane group. Oxyl and dodecyloxy.

Examples of the hydrocarbon group of R ^b1 include a C ₁ to C ₁₆ chain aliphatic hydrocarbon group, a C ₃ to C ₁₆ alicyclic hydrocarbon group, and a C ₆ to C ₁₈ aromatic hydrocarbon group.

Examples of Y having an alkyl group-containing alicyclic hydrocarbon group include the following groups.

Examples of Y having a hydroxyl group or a hydroxyl group-containing alicyclic hydrocarbon group include the following groups.

Examples of Y having an alicyclic hydrocarbon group containing an aromatic hydrocarbon group include the following groups.

Examples of Y having an alicyclic hydrocarbon group having a -(CH ₂ ) _j2 -O-CO-R ^b1 group include the following groups.

Y is preferably substituted with an adamantyl group by, for example, a hydroxyl group, and more preferably an adamantyl group and a hydroxyadamantyl group.

The sulfonic acid anion is preferably a divalent group represented by the formula (b1-1), and more preferably a group represented by the formula (b1-1-1) to the formula (b1-1-9).

In the formulae (b1-1-1) to (b1-1-9), Q ¹ , Q ² and L ^b2 represent the same as defined above (preferably, both Q ¹ and Q ² are fluorine atoms, and It is preferred that the group represented by the formula (b1-1) is L ^b2 ). R ^b2 and R ^b3 independently represent a C ₁ to C ₄ aliphatic hydrocarbon group or a hydroxyl group (preferably a methyl group or a hydroxyl group).

An example of a sulfonic acid anion having a chain aliphatic hydrocarbon group or an unsubstituted alicyclic hydrocarbon as Y, and a divalent group represented by the formula (b1-1) as L ^a1 includes the following anions.

By having - the substituent _{(CH 2) j2 -CO-OR} b1 alicyclic hydrocarbon group as Y, and the formula (b1-1) shown as examples of the divalent group L ^a1 of the sulfonic acid anion, comprising the following anions.

Examples of the sulfonic acid anion having a hydroxy group-substituted alicyclic hydrocarbon group as Y and a divalent group represented by the formula (b1-1) as L ^a1 include the following anions.

An example of a sulfonic acid anion having an aliphatic hydrocarbon group substituted with an aromatic hydrocarbon group or an aralkyl group as Y and a divalent group represented by the formula (b1-1) as a La ^a1 includes the following anions.

Examples of the sulfonic acid anion having a cyclic ether group as Y and a divalent group represented by the formula (b1-1) as L ^a1 include the following anions.

An example of a sulfonic acid anion having a lactone ring as Y and a divalent group represented by the formula (b1-1) as L ^a1 includes the following anions.

An example of a sulfonic acid anion having a cycloketone group as Y and a divalent group represented by the formula (b1-1) as L ^a1 includes the following anions.

An example having a sultone ring group as Y, and a divalent group represented by the formula (b1-1) as a sulfonate anion of L ^a1 includes the following anions.

Examples of the sulfonic acid anion having a chain aliphatic hydrocarbon group or an unsubstituted alicyclic hydrocarbon as Y, and a divalent group represented by the formula (b1-2) as L ^a1 include the following anions.

By having - the substituent _{(CH 2) j2 -CO-OR} b1 alicyclic hydrocarbon group as Y, and the formula (b1-2) shown in Examples of divalent anions of sulfonic acids as L ^a1, comprising the following anions.

An example of a sulfonic acid anion having a hydroxy-substituted alicyclic hydrocarbon group as Y and a divalent group represented by the formula (b1-2) as L ^a1 includes the following anions.

Examples of the sulfonate anion having an aliphatic hydrocarbon group substituted with an aromatic hydrocarbon group or an aralkyl group as Y, and a divalent group represented by the formula (b1-2) as a sulfonate anion of L ^a1 include the following anions.

An example of a sulfonic acid anion having a cyclic ether group as Y and a divalent group represented by the formula (b1-2) as L ^a1 includes the following anions.

An example of a sulfonic acid anion having a lactone ring as Y and a divalent group represented by the formula (b1-2) as L ^a1 includes the following anions.

An example of a sulfonic acid anion having a cyclic ketone group as Y and a divalent group represented by the formula (b1-2) as L ^a1 includes the following anions.

An example having a sultone ring group as Y, and a divalent group represented by the formula (b1-2) as a sulfonic acid anion of L ^a1 includes the following anions.

Examples of the sulfonic acid anion having a chain aliphatic hydrocarbon group as Y and a divalent group represented by the formula (b1-3) as L ^a1 include the following anions.

An example of a sulfonic acid anion having an alkoxy-substituted alicyclic hydrocarbon group as Y and a divalent group represented by the formula (b1-3) as L ^a1 includes the following anions.

An example of a sulfonic acid anion having a hydroxy-substituted alicyclic hydrocarbon group as Y and a divalent group represented by the formula (b1-3) as L ^a1 includes the following anions.

An example of a sulfonic acid anion having a cycloketone group as Y and a divalent group represented by the formula (b1-3) as L ^a1 includes the following anions.

Examples of the sulfonic acid anion having a chain aliphatic hydrocarbon group as Y and a divalent group represented by the formula (b1-4) as L ^a1 include the following anions.

Examples of the sulfonic acid anion having an alkoxy-substituted alicyclic hydrocarbon group as Y and a divalent group represented by the formula (b1-4) as L ^a1 include the following anions.

An example of a sulfonic acid anion having a hydroxy-substituted alicyclic hydrocarbon group as Y and a divalent group represented by the formula (b1-4) as L ^a1 includes the following anions.

An example of a sulfonic acid anion having a cycloketone group as Y and a divalent group represented by the formula (b1-4) as L ^a1 includes the following anions.

Among these, a sulfonic acid anion containing a divalent group represented by the formula (b1-1) as L ^a1 is preferred. Specific examples of preferred sulfonic acid anions include the following anions.

In particular, a sulfonate anion wherein C is optionally substituted with a C ₃ to C ₁₈ alicyclic hydrocarbon group is more preferred.

Examples of the cation of the acid generator (B) include a phosphonium cation such as a phosphonium cation, a phosphonium cation, an ammonium cation, a benzothiazolium cation, and a phosphonium cation. Among these, a phosphonium cation and a phosphonium cation are preferred, and an organic cation represented by any one of the formulae (b2-1) to (b2-4) is more preferable.

Z ^{+ of the} formula (B1) is preferably any one of the formulae (b2-1) to (b2-4).

Wherein R ^b4 to R ^b6 independently represent a C ₁ to C ₃₀ hydrocarbon group including a C ₁ to C ₃₀ alkyl group, a C ₃ to C ₁₈ alicyclic hydrocarbon group or a C ₆ to C ₁₈ aromatic hydrocarbon group, the alkyl group being a hydroxy group, a C ₁ to C ₁₂ alkoxy group or a C ₆ to C ₁₈ aromatic hydrocarbon group which may be substituted by a halogen atom, a C ₂ to C ₄ fluorenyl group and a epoxypropyloxy group, the aromatic The hydrocarbyl group may be substituted with a halogen atom, a hydroxyl group, a C ₁ to C ₁₈ alkyl group, a C ₃ to C ₁₈ alicyclic hydrocarbon group or a C ₁ to C ₁₂ alkoxy group; R ^b7 and R ^b8 independently represent a hydroxyl group at each occurrence, C ₁ to C ₁₂ alkyl or C ₁ to C ₁₂ alkoxy; m 2 and n 2 independently represent integers 0 to 5; R ^b9 and R ^b10 independently represent C ₁ to C ₁₈ alkyl or C ₃ to C ₁₈ lipid a cyclic hydrocarbon group; R ^b11 represents a hydrogen atom, a C ₁ to C ₁₈ alkyl group, a C ₃ to C ₁₈ alicyclic hydrocarbon group or a C ₆ to C ₁₈ aromatic hydrocarbon group; and R ^b12 represents a C ₁ to C ₁₈ hydrocarbon group including C ₁ to a C ₁₈ alkyl group, a C ₃ to C ₁₈ alicyclic hydrocarbon group or a C ₆ to C ₁₈ aromatic hydrocarbon group which may be a C ₁ to C ₁₂ alkyl group, a C ₁ to C ₁₂ alkoxy group, a C ₃ to C group ₁₈ or an alicyclic hydrocarbon group substituted with alkylcarbonyloxy; R ^b9 and R ^b10 may be bonded to form the sulfur-containing C ₃ to C ₁₂ cycloalkyl ( Best of C ₃ to C ₇ cycloalkyl), and contained in the ring -CH ₂ - may be -O -, - S- or -CO- substituted; R ^b11 and R ^b12 may be bonded to form a -CH-CO- containing a C ₃ to C ₁₂ ring (preferably a C ₄ to C ₇ ring), and -CH ₂ - contained in the ring may be replaced by -O-, -S- or -CO-; R ^b13 to R ^b18 Each occurrence is independently represented by a hydroxyl group, a C ₁ to C ₁₂ alkyl group or a C ₁ to C ₁₂ alkoxy group; L ^b11 represents -S- or -O-; o 2 , p 2 , s 2 and t 2 independently represent an integer 0 to 5; q2 or r2 independently represents integers 0 to 4; u2 represents integers 0 to 1.

Examples of the alkyl group, the alicyclic hydrocarbon group, the aromatic hydrocarbon group, the alkoxy group, the halogen atom and the fluorenyl group include the same as defined above.

Examples of the alkylcarbonyloxy group of R ^b12 include a methylcarbonyloxy group, an ethylcarbonyloxy group, a n-propylcarbonyloxy group, an isopropylcarbonyloxy group, a n-butylcarbonyloxy group, and a second butylcarbonyl group. Oxyl, tert-butylcarbonyloxy, pentylcarbonyloxy, hexylcarbonyloxy, octylcarbonyloxy and 2-ethylhexylcarbonyloxy.

Examples of preferred alkyl groups include methyl, ethyl, propyl, butyl, hexyl, octyl and 2-ethylhexyl groups, and especially the alkyl group of R ^b9 to R ^b11 is preferably a C ₁ to C ₁₂ alkane. base.

Examples of preferred alicyclic hydrocarbon groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclodecyl, 2-alkyladamantan-2-yl, 1-(adamantane-1 -alkyl)alkane-1-yl and isodecyl, especially the alicyclic hydrocarbon group of R ^b9 to R ^b11 is preferably a C ₃ to C ₁₈ alicyclic hydrocarbon group and more preferably a C ₄ to C ₁₂ alicyclic hydrocarbon group. .

Examples of preferred aromatic hydrocarbon groups include phenyl, 4-methoxyphenyl, 4-ethylphenyl, 4-tert-butylphenyl, 4-cyclohexylphenyl, 4-methoxyphenyl. , biphenyl and naphthyl.

Examples of alkyl-substituted aromatic groups are typically represented by aralkyl groups such as benzyl, phenethyl, phenylpropyl, trityl, naphthylmethyl, and naphthylethyl.

Examples of the ring formed by bonding R ^b9 and R ^{b10 to} each other include a thiolane-1-ium ring (tetrahydrothiophene ring), thiene (thian)-1-anthracene ring and 1,4-oxathiaxanthene-4-anthracene ring.

Examples of the ring formed by bonding R ^b11 and R ^{b12 to} each other include a pendant oxycycloheptane ring, a pendant oxycyclohexane ring, a pendant oxycyclodecane ring, and a pendant oxyadamantane ring.

Among the cations represented by the formulae (b2-1) to (b2-4), the cation represented by the formula (b2-1) is preferred, and the triphenylphosphonium cation is used (in the formula (b2-1-1) Wherein, v2=w2=x2=0) and the tolylguanidine cation (in the formula (b2-1-1), v2=w2=x2=1, and R ^b19 , R ^b20 and R ^b21 are methyl) Better.

Wherein, each of R ^b19 to R ^b21 independently represents a halogen atom, a hydroxyl group, a C ₁ to C ₁₈ aliphatic hydrocarbon group or a C ₁ to C ₁₂ alkoxy group; and v 2 to x 2 independently represent an integer of 0 to 5.

The aliphatic hydrocarbon group is preferably a C ₁ to C ₁₂ alkyl group or a C ₄ to C ₁₈ alicyclic hydrocarbon group.

In formula (b2-1-1), R ^b19 to R ^b21 independently represents preferably a halogen atom (and more preferably fluorine atom), a hydroxyl group, a C ₁ to C ₁₂ alkyl or a C ₁ to C ₁₂ alkoxy And v2 to x2 independently represent preferably 0 or 1.

Specific examples of the cation of the formula (b2-1-1) include the following cations.

When the resist composition includes the acid generator (B1) having such organic cations, a favorable focus limit can be caused in the production of the resist pattern.

Specific examples of the cation of the formula (b2-2) include the following cations.

Specific examples of the cation of the formula (b2-3) include the following cations.

Specific examples of the cation of the formula (b2-4) include the following cations.

The acid generator (B1) is a compound of the above-mentioned combination of a sulfonic acid anion and an organic cation.

The above sulfonic acid anion and organic cation may be combined as needed, and any combination of an anion represented by formula (b1-1-1) to formula (b1-1-9) and a cation represented by formula (b2-1-1), And any combination of the anion represented by the formula (b1-1-3) to the formula (b1-1-5) and the cation represented by the formula (b2-3) is preferred.

The preferred acid generator (B1) is a salt of the formula (B1-1) to the formula (B1-17). Among these, formula (B1-1), (B1-2), (B1-3), (B1-6), (B1-11) containing a triphenylphosphonium cation or a trimethylphenylphosphonium cation. (B1-12), (B1-13), and (B1-14) are preferred, and the formulae (B1-1), (B1-2), (B1-3), (B1-11), and (B1) -12) is better.

<Basic compound (hereinafter may be referred to as "basic compound (C)">

The resist composition of the present invention may contain a basic compound (C). The basic compound (C) is a compound having a property of quenching the acid generated by the acid generator, and is referred to as a "quenching agent".

As the basic compound (C), a nitrogen-containing basic compound (for example, an amine and ammonium hydroxide) is preferred. The amine can be an aliphatic amine or an aromatic amine. The aliphatic amine includes any of a primary amine, a secondary amine, and a tertiary amine. The aromatic amine includes an amine in which an amine group is bonded to an aromatic ring such as aniline, and a heteroarylamine such as pyridine.

The preferred basic compound (C) includes an aromatic amine represented by the formula (C2), particularly an aromatic amine represented by the formula (C2-1).

Wherein Ar ^c1 represents an aromatic hydrocarbon group: R ^c5 and R ^c6 independently represent a hydrogen atom, an aliphatic hydrocarbon group (preferably a C ₁ to C ₆ chain aliphatic hydrocarbon group (ie, an alkyl group) or a C ₅ to C ₁₀ alicyclic ring. a hydrocarbon group (ie, a cycloalkyl group) or an aromatic hydrocarbon group, and the hydrogen atom contained in the aliphatic hydrocarbon group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group may be replaced by a hydroxyl group, an amine group or a C ₁ to C ₆ alkoxy group. The hydrogen atom contained in the amine group may be replaced by a C ₁ to C ₄ alkyl group: R ^c7 independently represents a chain aliphatic hydrocarbon group (preferably a C ₁ to C ₆ alkyl group), C ₁ to each occurrence. a C ₆ alkoxy group, an alicyclic hydrocarbon group (preferably a C ₅ to C ₁₀ alicyclic hydrocarbon group, and more preferably a C ₅ to C ₁₀ cycloalkyl group) or an aromatic hydrocarbon group (preferably a C ₆ to C ₁₀ aromatic group) a hydrocarbon group, the hydrogen atom contained in the aliphatic hydrocarbon group, the alkoxy group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group may be replaced by a hydroxyl group, an amine group or a C ₁ to C ₆ alkoxy group, which is contained in the amine group The hydrogen atom may be replaced by a C ₁ to C ₄ alkyl group; m 3 represents an integer of 0 to 3.

The aliphatic hydrocarbon group preferably has C ₁ to C ₆ , the alicyclic hydrocarbon group preferably has C ₅ to C ₁₀ , the aromatic hydrocarbon group preferably has C ₆ to C ₁₀ ; and the alkoxy group is preferably To have C ₁ to C ₆ .

Specific examples of the aromatic amine represented by the formula (C2) include 1-naphthylamine and 2-naphthylamine.

Specific examples of the aniline represented by the formula (C2-1) include aniline, diisopropylaniline, 2-, 3- or 4-methylaniline, 4-nitroaniline, N-methylaniline, N,N-di Methyl aniline, and diphenylamine.

Further, examples of the basic compound (C) include compounds represented by the formula (C3) to the formula (C11);

Wherein R ^c8 , R ^c20 , R ^c21 , R ^c23 , R ^c24 , R ^c25 , R ^c26 , R ^c27 and R ^c28 independently represent any of the ^groups as recited in R ^c7 ; R ^c9 to R ^c14 , R ^c16 To R ^c19 and R ^c22 independently represent any of the groups as recited in R ^c5 and R ^c6 ; R ^c15 independently represents an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an alkanoyl at each occurrence; n3 represents Integer 0 to 8; o3 to u3 independently represent integers 0 to 3; L ^c1 and L ^c2 independently represent a divalent aliphatic hydrocarbon group (preferably a C ₁ to C ₆ aliphatic hydrocarbon group, and more preferably C ₁ to C) ₆ alkanediyl), -CO-, -C(=NH)-, -C(=NR ^c3 )-, -S-, -SS- or a combination thereof; R ^c3 represents a C ₁ to C ₄ alkyl group .

The aliphatic hydrocarbon group of R ^c15 is preferably a C ₁ to C ₆ aliphatic hydrocarbon group, the alicyclic hydrocarbon group is preferably a C ₃ to C ₆ alicyclic hydrocarbon group, and the alkano group is preferably a C ₂ to C ₆ alkyl fluorenyl group.

Examples of the alkyl fluorenyl group include an ethyl fluorenyl group, a 2-methylethyl fluorenyl group, a 2,2-dimethylethenyl group, a propyl fluorenyl group, a butyl fluorenyl group, an isobutyl fluorenyl group, a pentyl group, and a 2,2-dimethyl group.醯基.

Specific examples of the compound represented by the formula (C3) include, for example, hexylamine, heptylamine, octylamine, decylamine, decylamine, dibutylamine, diamylamine, dihexylamine, diheptylamine, dioctylamine, and Indoleamine, diamine, triethylamine, trimethylamine, tripropylamine, tributylamine, triamylamine, trihexylamine, triheptylamine, trioctylamine, tridecylamine, tridecylamine, methyldibutylamine , methyl dipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldiamine,methyldiamine,ethyldibutylamine, Ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldiamine,ethyldiamine,dicyclohexylmethylamine, ginseng[2-(2-A) Oxyethoxyethyl)ethyl]amine, triisopropanolamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diamino-1,2-di Phenylethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane and 4,4'-diamino-3,3'-diethyldiphenylmethane.

Specific examples of the compound represented by the formula (C4) include, for example, a piperidine (piperazine).

Specific examples of the compound represented by the formula (C5) include, for example, morpholine.

Specific examples of the compound represented by the formula (C6) include, for example, a piperidine (piperizine), as described in JP H11-52575-A A hindered amine compound of the skeleton.

Specific examples of the compound represented by the formula (C7) include, for example, 2,2'-methylenebisaniline.

Specific examples of the compound represented by the formula (C8) include, for example, imidazole and 4-methylimidazole.

Specific examples of the compound represented by the formula (C9) include, for example, pyridyl And 4-methylpyrrol .

Specific examples of the compound represented by the formula (C10) include, for example, 1,2-bis(2-pyridyl)ethane, 1,2-bis(4-pyridyl)ethane, 1,2-di (2) -pyridyl)ethene, 1,2-bis(4-pyridyl)ethene, 1,3-bis(4-pyridyl)propane, 1,2-bis(4-pyridyloxy)ethane, di( 2-pyridyl)one, 4,4'-dipyridyl sulfide, 4,4'-dipyridyl disulfide, 2,2'-dipyridylamine and 2,2'-diaminomethylpyridine (dipicolylamine).

Specific examples of the compound represented by the formula (C11) include, for example, bipyridine.

Examples of ammonium hydroxide include tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, phenyltrimethylammonium hydroxide , 3-(trifluoromethyl)phenyltrimethylammonium hydroxide, tetra-n-butylsalicylate ammonium, and choline.

Among these, diisopropylaniline (especially 2,6-diisopropylaniline) is preferred as the basic compound (C) contained in the resist compound of the present invention.

<Solvent (hereinafter referred to as "solvent (D)">

The resist composition of the present invention may include a solvent (D). The solvent (D) is preferably a kind and amount according to a resin (A) having a structural unit derived from the compound (a) (that is, a resin (AA) or a resin (AB)) from the viewpoint of good coating properties. And the type and amount of the acid generator are selected.

Examples of the solvent (D) include glycol ether esters such as ethyl acesulfame acetate, acesulfame acetate, and propylene glycol monomethyl ether acetate; ethers such as diethylene glycol dimethyl ether; esters such as Ethyl lactate, butyl acetate, amyl acetate, and ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone, and cyclohexanone; and cyclic esters such as γ-butyrolactone. These solvents may be used in a single solvent or as a mixture of two or more solvents.

<Other ingredients (hereinafter, it can be called "other ingredients (F)">

The resist composition may also include various additives as necessary. Examples of the other component (F) include a sensitizer, a dissolution inhibitor, a surfactant, a stabilizer, and a dye.

<Preparation of Resist Composition>

The resist composition of the present invention can be prepared by mixing a resin (A) (particularly a resin (AA)) and an acid generator (B), or by mixing a resin (A) (particularly a resin (AA)), The acid generator (B1) and the basic compound (C), and if necessary, the solvent (D) and other components (F) are prepared. The order of mixing is not particularly limited. Mixing can be done in any order. According to the kind of the resin having the structural unit derived from the compound (a), and the solubility of the resin having the structural unit derived from the compound (a) in the solvent (D), the mixing temperature can be adjusted in the range of 10 to 40 ° C To the proper temperature. Depending on the temperature of the mixing, the mixing time can be adjusted to an appropriate time in the range of 0.5 to 24 hours. The appliance used for mixing is not particularly limited. Stirring mixing can be used.

After mixing the above ingredients, the resist composition of the present invention can be prepared by filtering the mixture through a filter having a pore size of about 0.01 to 0.2 μm.

When the resin (AA) is used as the resin (A), the resist composition of the present invention preferably contains 80% by weight or more and 99% by weight or less of the resin (A) based on the total solid ratio of the resist composition. .

When the resin (AB) is used as the resin (A), the resist composition of the present invention preferably contains 0.1% by weight or more and 10% by weight or less of the resin (A) based on the total solid ratio of the resist composition. .

In this specification, the term "solid ratio of the resist composition" means the entire ratio of all components except the solvent (D). For example, if the ratio of the solvent (D) is 90% by weight, the solid ratio of the resist composition is 10% by weight.

In the resist composition of the present invention, the ratio of the acid generator (B) is preferably 1 part by weight or more (and more preferably 3 parts by weight or more) based on 100 parts by weight of the resin (A), and It is also preferably 30 parts by weight or less (and more preferably 25 parts by weight or less).

When the resin (AB) and the resin (X) are used instead of the resin (AA) as the resin (A), the ratio of the acid generator (B) is preferably 1 part by weight or more based on 100 parts by weight of the resin (X) ( And more preferably 3 parts by weight or more, and also preferably 30 parts by weight or less (and more preferably 25 parts by weight or less).

When the resist composition includes the basic compound (C), the proportion thereof is preferably from 0.01 to 1% by weight based on the total solid ratio of the resist composition.

The ratio of the solvent may be adjusted depending on the kind of the resin (A), and may be 90% by weight or more, preferably 92% by weight or more, and more preferably 94% by weight or more, and still more preferably 99.9% by weight. % or less, and more preferably 99% by weight or less. If the resist composition contains a solvent in this range, the resist composition is preferably used to form a thin resist film which can be used to form a composition layer of 30 to 300 nm thick.

The ratio of the resin (A), the acid generator (B), the basic compound (C), and the solvent (D) can be adjusted according to the components used in the preparation of the resist composition of the present invention, and in the preparation of the present invention. The resist composition of the invention can be measured by known analytical methods such as liquid chromatography and gas chromatography.

If the resist composition of the present invention has other components (F), the proportion thereof may be adjusted depending on the kind thereof.

<Method of forming a resist pattern>

A method of forming a resist pattern of the present invention, comprising the steps of:

(1) applying the resist composition of the present invention to a substrate;

(2) drying the applied composition to form a composition layer;

(3) exposing the composition layer using an exposure device;

(4) heating the exposed composition layer, and

(5) Developing the heated composition layer with a developing device.

Application of the resist composition to the substrate can typically be carried out by using a resist application device, such as a spin coater known in the art of semiconductor micromachining technology. The thickness of the resist composition layer applied can be adjusted by adjusting the variable conditions of the resist application device. These conditions can be selected in accordance with pre-executed pre-experiments. The substrate can be selected from a variety of substrates for micromachining. The substrate may be cleaned and an organic anti-reflective film may be formed on the substrate by using a commercially available anti-reflective composition prior to application of the resist composition.

The applied composition layer is dried, for example, using a heating device such as a heating plate (so-called "prebake"), a pressure reducing device, or a combination thereof. Therefore, the solvent self-resistant composition evaporates and forms a composition layer as the solvent is removed. The conditions of the heating device or the pressure reducing device can be adjusted depending on the kind of the solvent to be used. The temperature in this case is usually in the range of 50 to 200 °C. Further, the pressure is usually in the range of 1 to 1.0 × 10 ⁵ Pa.

The composition layer thus obtained is usually exposed using an exposure device or a liquid infiltration exposure device. Exposure is typically performed by a mask corresponding to the pattern to be obtained. Various types of exposure light sources can be used, such as ultraviolet laser excitation such as KrF excitation laser (wavelength: 248 nm), ArF excitation laser (wavelength: 193 nm), F ₂ excitation laser (wavelength: 157 nm) illumination, or The far-ultraviolet wavelength-converted laser light from a solid-state laser source (YAG or semiconductor laser or the like), or vacuum-ultraviolet coherent laser or the like. Further, the exposure device may be one that emits an electron beam or extreme ultraviolet light (EUV).

The composition layer may be formed of an exposed portion and an unexposed portion, and the above exposure is performed by transmitting the mask. In the exposed portion, the acid is produced by receiving the energy of the exposure by the acid generator contained in the resist composition. Therefore, the acid labile group contained in the resin (AA) or the resin (X) reacts with an acid to eliminate the protecting group. As a result, the resin of the exposed portion in the composition layer becomes soluble in the alkaline aqueous solution. On the other hand, in the unexposed portion, the resin (AA) or the resin (X) is still insoluble or poorly soluble in the alkaline aqueous solution due to no exposure. As a result, the solubility of the composition layer in the exposed portion and the composition layer in the unexposed portion in the alkaline solution will be different.

After the exposure, the composition layer is subjected to heat treatment (so-called "post exposure baking") to promote the deprotection reaction. The heating reaction can be carried out using a heating device such as a heating plate. The heating temperature is usually in the range of 50 to 200 ° C, preferably in the range of 70 to 150 ° C.

The composition layer is developed after the heat treatment, usually in an alkaline developing solution and using a developing device. Development here means that the composition layer is contacted with an alkaline solution after heat treatment. Therefore, the exposed portion of the composition layer is dissolved and removed by the alkaline solution, and the unexposed portion of the composition layer remains on the substrate, thereby forming a resist pattern. Here, as the alkaline developing solution, various types of aqueous alkaline solutions used in the field can be used. Examples include aqueous solutions of tetramethylammonium hydroxide and (2-hydroxyethyl)trimethylammonium hydroxide (common name: choline).

After development, it is preferred to rinse the substrate and pattern with ultrapure water and remove any water remaining thereon.

According to the method of producing a resist pattern of the present invention, it is possible to form a resist pattern having an excellent MEF and the pattern has fewer defects.

<application>

The resist composition of the present invention is useful as a resist composition for exciting laser lithography such as ArF, KrF or the like, and for electron beam (EB) exposure lithography and extreme ultraviolet light. (EUV) exposure lithography, can also be used for liquid infiltration exposure lithography.

The resist compositions of the present invention are useful in semiconductor micromachining and in the fabrication of liquid crystal, thermal print heads for circuit boards, and the like, and are further suitable for use in other photolithography processes over a wide range of applications.

Example

The invention will be more specifically described by the examples, which are not intended to limit the scope of the invention.

All percentages and parts of the ratios or amounts used in the examples and comparative examples are by weight unless otherwise specified.

The structure of the compound was confirmed by mass analysis (LC: Agilent Model 1100, MASS: Agilent LC/MSD type or LC/MSD TOF type).

The weight average molecular weight is a value determined by gel permeation chromatography using polystyrene as a standard product.

Column: TSKgel Multipore HXL-Mx3 Link + Protection String (Tosoh Co. 1td.)

Washing solution: tetrahydrofuran

Flow rate: 1.0 mL/min

Detection device: RI detector

Column temperature: 40 ° C

Injection volume: 100μL

Standard material for calculating weight molecular weight: standard polystyrene (Tosoh Co., 1td.)

Synthesis Example 1: Synthesis of Compound (I)

10.00 parts of the compound (I-2), 40.00 parts of tetrahydrofuran, and 7.29 parts of pyridine were placed in the reactor, and stirred at 23 ° C for 30 minutes. The obtained mixture was cooled to 0 °C. While maintaining the same temperature, 33.08 parts of the compound (I-1) was added to the mixture over 1 hour. The temperature of the mixture was then raised to about 23 ° C and the mixture was stirred at the same temperature for 3 hours. 371.51 parts of ethyl acetate and 20.19 parts of a 5% hydrochloric acid solution were added to the obtained reactant, and stirred at 23 ° C for 30 minutes. Next, after standing to separate the layers, the obtained solution was separated to recover an organic layer. 81.42 parts of saturated sodium hydrogencarbonate was added to the organic layer, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, and then separated to recover an organic layer. 90.38 parts of ion-exchanged water was added to the recovered organic layer, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, and then separated, and the organic layer was washed with water. Repeat the operation of washing with water 5 times. The obtained organic layer was concentrated to give 23.40 parts of Compound (I).

MS (mass spectrometry): 326.0 (molecular ion peak)

Synthesis Example 2: Synthesis of Compound (J)

8.50 parts of the compound (J-2), 34.00 parts of tetrahydrofuran, and 6.20 parts of pyridine were placed in the reactor, and stirred at 23 ° C for 30 minutes. The obtained mixture was cooled to 0 °C. While maintaining the same temperature, 13.78 parts of the compound (J-1) was added to the mixture over 1 hour. The temperature of the mixture was then raised to about 23 ° C and the mixture was stirred at the same temperature for 3 hours. 249.91 parts of ethyl acetate and 17.16 parts of 5% hydrochloric acid were added to the obtained reactant, and stirred at 23 ° C for 30 minutes. Next, after standing to separate the layers, the obtained solution was separated to recover an organic layer. 62.62 parts of saturated sodium hydrogencarbonate was added to the recovered organic layer, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, and then separated to recover an organic layer. 62.62 parts of ion-exchanged water was added to the recovered organic layer, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, and then separated, and the organic layer was washed with water. Repeat the operation of washing with water 5 times. The obtained organic layer was concentrated, and then the obtained concentrate was fractionated by a column (condition: a fixed bed of 60 to 200 mesh of silica gel manufactured by Merck, ethyl acetate as a developing solvent) to give 13.00 parts. Compound (J-3).

13.00 parts of the compound (J-3), 39.00 parts of isopropyl alcohol and 0.20 parts of sulfuric acid were placed in the reactor, and stirred at 85 ° C for 3 hours. The obtained reactant was cooled to 23 °C. 156.59 parts of ethyl acetate and 42.00 parts of saturated sodium hydrogencarbonate were added to the obtained reactant, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, and then separated to recover an organic layer. . 39.15 parts of ion-exchanged water was added to the recovered organic layer, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, and then separated, and the organic layer was washed with water. Repeat the operation of washing with water 5 times. The obtained organic layer was concentrated, and then the obtained concentrate was fractionated by a column (condition: a fixed bed of 60 to 200 mesh of silicone manufactured by Merck, n-heptane / ethyl acetate = 1 / 1 as a developing solvent ), 11.64 parts of the compound (J) were produced.

MS (mass spectrometry): 394.1 (molecular ion peak)

Synthesis Example 3: Synthesis of Compound (O)

88.00 parts of the compound (O-2), 616.00 parts of methyl isobutyl ketone, and 60.98 parts of pyridine were mixed while stirring at 23 ° C for 30 minutes. The obtained mixture was cooled to 0 °C. While maintaining the same temperature, 199.17 parts of the compound (O-1) was added to the mixture over 1 hour. The temperature of the mixture was then raised to about 10 ° C, and the mixture was stirred at the same temperature for 1 hour. The obtained reactant was added to 1446.22 parts of n-heptane and 703.41 parts of a 2% hydrochloric acid solution to obtain a mixture, and the mixture was stirred at 23 ° C for 30 minutes. The obtained solution was allowed to stand for stratification, followed by separation to recover the organic layer. To the organic layer, 337.64 parts of a 2% hydrochloric acid solution was added, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, and then separated to recover an organic layer. To the recovered organic layer, 361.56 parts of ion-exchanged water was added, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, and then separated, and the organic layer was washed with water. To the organic layer, 443.92 parts of a 10% aqueous potassium carbonate solution was added, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, and then separated to recover an organic layer. Repeat this operation twice. To the recovered organic layer, 361.56 parts of ion-exchanged water was added, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, and then separated, and the organic layer was washed with water. Repeat the operation of washing with water 5 times. The obtained organic layer was concentrated to give 163.65 parts of compound (O).

MS (mass spectrometry): 276.0 (molecular ion peak)

Synthesis Example 4: Synthesis of Compound (P)

80.00 parts of the compound (P-2), 560.00 parts of methyl isobutyl ketone, and 58.35 parts of pyridine were mixed while stirring at 23 ° C for 30 minutes. The obtained mixture was cooled to 0 °C. While maintaining the same temperature, 135.57 parts of the compound (P-1) was added to the mixture over 1 hour, the temperature was raised to about 10 ° C, and the mixture was stirred at the same temperature for 1 hour. To the obtained reactant were added 2084.79 parts of ethyl acetate, 323.10 parts of a 5% hydrochloric acid solution, and 521.20 parts of ion-exchanged water, and the mixture was stirred at 23 ° C for 30 minutes. The obtained solution was allowed to stand for stratification, followed by separation to recover the organic layer. 521.20 parts of ion-exchanged water was added to the recovered organic layer, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, and then separated, and the organic layer was washed with water. To the organic layer after washing, 267.63 parts of a 10% aqueous potassium carbonate solution was added, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, and then separated to wash the organic layer. Repeat this cleaning operation twice. 521.20 parts of ion-exchanged water was added to the recovered organic layer, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, and then separated, and the organic layer was washed with water. This washing operation was repeated 4 times. The obtained organic layer was concentrated to give 130.40 parts of Compound (P).

MS (mass spectrometry): 226.1 (molecular ion peak)

Synthesis Example 5: Synthesis of Compound (Q)

9.60 parts of the compound (Q-2), 38.40 parts of tetrahydrofuran, and 5.99 parts of pyridine were mixed and stirred at 23 ° C for 30 minutes. The obtained mixture was cooled to 0 °C. While maintaining the same temperature, 14.00 parts of the compound (Q-1) was added to the mixture over 1 hour. The temperature of the mixture was then raised to about 10 ° C and stirred at the same temperature for 1 hour. To the thus obtained reactant containing the compound (Q-3), 14.51 parts of the compound (Q-4) (1-(3-dimethylaminopropyl)-3-ethylcarbodiimide was added. The hydrochloride salt and 8.20 parts of the compound (Q-5) were stirred at 23 ° C for 3 hours. 271.95 parts of ethyl acetate and 16.57 parts of a 5% hydrochloric acid solution were added to the obtained reactant solution, and stirred at 23 ° C for 30 minutes. Next, after standing to separate the layers, the obtained solution was separated to recover an organic layer. 63.64 parts of saturated sodium hydrogencarbonate was added to the recovered organic layer, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, and then separated to wash the organic layer. Repeat this cleaning operation twice. 67.99 parts of ion-exchanged water was added to the organic layer after washing, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, and then separated, and the organic layer was washed with water. Repeat the operation of washing with water 5 times. The obtained organic layer was concentrated, and 107.71 parts of ethyl acetate was added to the concentrate thus obtained, and stirred until completely dissolved. Thereafter, 646.26 parts of n-heptane was added thereto in the form of droplets. Then, the obtained solution was stirred at 23 ° C for 30 minutes, and filtered to give 15.11 parts of the compound (Q).

MS (mass spectrometry): 486.2 (molecular ion peak)

Synthesis Example 6: Synthesis of Compound (R)

5.00 parts of the compound (R-1), 20.00 parts of dimethylformamide and 2.30 parts of potassium carbonate were mixed and stirred at 40 ° C for 1 hour. To the reaction mixture containing the compound (R-2) thus obtained, 6.59 parts of the compound (R-3) was added, and the obtained mixture was stirred at 60 ° C for 10 hours. The reactant solution thus obtained was added to 100.00 parts of ethyl acetate and 24.30 parts of a 5% hydrochloric acid solution to obtain a mixture, and the reaction was stirred at 23 ° C for 30 minutes. The obtained solution was allowed to stand for stratification, followed by separation to recover the organic layer. 50.00 parts of ion-exchanged water was added to the organic layer, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, then separated, and the organic layer was washed with water. Repeat the operation of washing with water 5 times. The obtained organic layer was concentrated to give 5.70 parts of Compound (R-4).

5.70 parts of the obtained compound (R-4), 3.70 parts of the compound (R-5), 36.47 parts of toluene and 0.05 parts of sulfuric acid were mixed, and the obtained reactant was thermally dried at 115 ° C for 6 hours. The obtained reaction solution was cooled, and 200.00 parts of ethyl acetate, 125.00 parts of ion-exchanged water, and 3.00 parts of sodium hydrogencarbonate were added thereto, and the obtained solution was stirred at 23 ° C for 30 minutes, and allowed to stand. After the layer, it is then separated to recover the organic layer. To the recovered organic layer, 125.00 parts of ion-exchanged water was added, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, and then separated, and the organic layer was washed with water. Repeat the operation of washing with water 5 times. The obtained organic layer was concentrated, and then the obtained concentrate was fractionated by a column (condition: a fixed bed of 60 to 200 mesh of silica gel manufactured by Merck, ethyl acetate as a developing solvent) to give 4.82 parts of a compound ( R).

MS (mass spectrometry): 386.2 (molecular ion peak)

Synthesis Example 7: Synthesis of Compound (U)

33.25 parts of the compound (U-1), 23.93 parts of dichlorohexylcarbodiimide, and 40.00 parts of dichloromethane were placed in the reactor and mixed. The obtained mixture was cooled to 0 ° C, and 18.83 parts of the compound (U-2) was added thereto. The mixture was stirred at 0 ° C for 1 hour. The temperature of the mixture was then raised to about 23 ° C and the mixture was stirred for 30 minutes. The mixture was filtered to remove undissolved material, and the obtained filtrate was concentrated to give 44.19 parts of compound (U-3).

19.33 parts of the obtained compound (U-3), 19.02 parts of the compound (U-4) and 200 parts of acetonitrile were placed in a reactor, mixed and stirred at 50 ° C for 3 hours. The obtained mixture was concentrated, and 300 parts of chloroform and 150 parts of ion-exchanged water were added thereto. The obtained solution was separated to recover an organic layer. The recovered organic layer was washed with 150 parts of ion-exchanged water and concentrated. The obtained concentrate was fractionated by a column (condition: a fixed phase of a silica gel of 60 to 200 mesh manufactured by Merck, ethyl acetate as a developing solvent) to give 14.58 parts of a compound (U).

MS (mass spectrometry): 315.1 (molecular ion peak)

Synthesis Example 8: Synthesis of Compound (X)

6.32 parts of the compound (X-2), 30.00 parts of tetrahydrofuran, and 5.99 parts of pyridine were mixed while stirring at 23 ° C for 30 minutes. The obtained mixture was cooled to 0 °C. While maintaining the same temperature, 14.00 parts of the compound (X-1) was added to the mixture over 1 hour. The temperature of the mixture was then raised to about 10 ° C and the mixture was stirred at the same temperature for 1 hour. To the thus obtained reactant containing the compound (X-3), 14.51 parts of the compound (X-4) (1-(3-dimethylaminopropyl)-3-ethylcarbodiimide salt was added. The acid salt) and 8.20 parts of the compound (X-5) were stirred at 23 ° C for 3 hours. 270 parts of ethyl acetate and 16.57 parts of a 5% hydrochloric acid solution were added to the obtained reactant solution, and stirred at 23 ° C for 30 minutes. Then, after standing to separate the layers, the obtained solution was separated to recover the organic layer. 65 parts of saturated sodium hydrogencarbonate was added to the recovered organic layer, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, and then separated to wash the organic layer. Repeat this cleaning operation twice. 65 parts of ion-exchanged water was added to the organic layer after washing, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, and then separated, and the organic layer was washed with water. Repeat the operation of washing with water 5 times. The obtained organic layer was concentrated, and then the obtained concentrate was fractionated by a column (condition: a fixed phase of a silica gel of 60 to 200 mesh manufactured by Merck, n-heptane / ethyl acetate as a developing solvent) to give 9.90. Part of the compound (X).

MS (mass spectrometry): 434.1 (molecular ion peak)

Synthesis Example 9: Synthesis of Compound (Y)

7.08 parts of the compound (Y-2), 30.00 parts of tetrahydrofuran, and 5.99 parts of pyridine were mixed and stirred at 23 ° C for 30 minutes. The obtained mixture was cooled to 0 °C. While maintaining the same temperature, 14.00 parts of the compound (Y-1) was added to the mixture over 1 hour. The temperature of the mixture was then raised to about 10 ° C, and the mixture was stirred at the same temperature for 1 hour. To the thus obtained reactant containing the compound (Y-3), 14.51 parts of the compound (Y-4) (1-(3-dimethylaminopropyl)-3-ethylcarbodiimide salt was added. The acid salt) and 8.20 parts of the compound (Y-5) were stirred at 23 ° C for 3 hours. 270 parts of ethyl acetate and 16.57 parts of a 5% hydrochloric acid solution were added to the obtained reactant solution, and stirred at 23 ° C for 30 minutes. Next, after standing to separate the layers, the obtained solution was separated to recover an organic layer. 65 parts of saturated sodium hydrogencarbonate was added to the recovered organic layer, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, and then separated to wash the organic layer. Repeat this cleaning operation twice. 65 parts of ion-exchanged water was added to the washed organic layer, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, and then separated, and the organic layer was washed with water. Repeat the operation of washing with water 5 times. The obtained organic layer was concentrated, and then the obtained concentrate was fractionated by a column (condition: a fixed phase of a silica gel of 60 to 200 mesh manufactured by Merck, n-heptane/ethyl acetate as a developing solvent) to give 10.24. Parts of the compound (Y).

MS (mass spectrometry): 446.1 (molecular ion peak)

Synthesis Example 10: Synthesis of Compound (Z)

7.33 parts of the compound (Z-2), 30.00 parts of tetrahydrofuran, and 5.99 parts of pyridine were mixed while stirring at 23 ° C for 30 minutes. The obtained mixture was cooled to 0 °C. While maintaining the same temperature, 14.00 parts of the compound (Z-1) was added to the mixture over 1 hour. The temperature of the mixture was raised to about 10 ° C, and the mixture was stirred at the same temperature for 1 hour. To the thus obtained reactant containing the compound (Z-3), 14.51 parts of the compound (Z-4) (1-(3-dimethylaminopropyl)-3-ethylcarbodiimide salt was added. The acid salt) and 8.20 parts of the compound (Z-5) were stirred at 23 ° C for 3 hours. 270 parts of ethyl acetate and 16.57 parts of a 5% hydrochloric acid solution were added to the obtained reactant solution, and stirred at 23 ° C for 30 minutes. Then, after standing to separate the layers, the obtained solution was separated to recover the organic layer. 65 parts of saturated sodium hydrogencarbonate was added to the recovered organic layer, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, and then separated to wash the organic layer. This cleaning operation was repeated twice. 65 parts of ion-exchanged water was added to the organic layer after washing, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, and then separated, and the organic layer was washed with water. Repeat the operation of washing with water 5 times. The obtained organic layer was concentrated, and then the obtained concentrate was fractionated by a column (condition: a fixed phase of a silica gel of 60 to 200 mesh manufactured by Merck, n-heptane/ethyl acetate as a developing solvent) to give 10.24. Parts of the compound (Z).

MS (mass spectrometry): 450.2 (molecular ion peak)

Synthesis Example 11: Synthesis of Compound (ZA)

10.40 parts of the compound (ZA-2), 72.80 parts of methyl isobutyl ketone, and 7.21 parts of pyridine were mixed while stirring at 23 ° C for 30 minutes. The obtained mixture was cooled to 0 °C. While maintaining the same temperature, 20.08 parts of the compound (ZA-1) was added to the mixture over 1 hour. The temperature of the mixture was then raised to about 10 ° C, and the mixture was stirred at the same temperature for 1 hour. The reactant thus obtained was added to 220.97 parts of n-heptane, 99.76 parts of a 2% hydrochloric acid solution to obtain a mixture, and the mixture was stirred at 23 ° C for 30 minutes. The obtained solution was allowed to stand for stratification, and then it was separated to recover an organic layer. 39.90 parts of a 5% hydrochloric acid solution was added to the recovered organic layer, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, and then separated to recover an organic layer. To the recovered organic layer, 55.34 parts of ion-exchanged water was added, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, then separated, and the organic layer was washed with water. To the organic layer after washing, 73.45 parts of a 10% aqueous potassium carbonate solution was added, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, and then separated to wash the organic layer. Repeat this operation twice. 110.68 parts of ion-exchanged water was added to the organic layer after washing, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, and then separated, and the organic layer was washed with water. This washing operation was repeated 4 times. The obtained organic layer was concentrated to give 22.02 parts of Compound (ZA).

MS (mass spectrometry): 358.1 (molecular ion peak)

Synthesis Example 12: Synthesis of Compound (ZB)

30.00 parts of the compound (ZB-2), 210.00 parts of methyl isobutyl ketone, and 18.00 parts of pyridine were mixed while stirring at 23 ° C for 30 minutes. The obtained mixture was cooled to 0 °C. While maintaining the same temperature, 48.50 parts of the compound (ZB-1) was added to the mixture over 1 hour. The temperature of the mixture was then raised to about 5 ° C, and the mixture was stirred at the same temperature for 1 hour. The reactant thus obtained was added to 630 parts of ethyl acetate, 99.68 parts of a 5% hydrochloric acid solution, and 126 parts of ion-exchanged water to obtain a mixture, and the mixture was stirred at 23 ° C for 30 minutes. The obtained solution was allowed to stand for stratification, which was then separated and the organic layer was recovered. To the recovered organic layer, 86.50 parts of a 10% aqueous potassium carbonate solution was added, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, and then separated to wash the organic layer. Repeat this operation twice. 157.50 parts of ion-exchanged water was added to the organic layer after washing. The obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, then separated, and the organic layer was washed with water. Repeat the operation of washing with water 5 times. The obtained organic layer was concentrated to give 27.61 parts of compound (ZB).

MS (mass spectrometry): 354.1 (molecular ion peak)

Synthesis Example 13: Synthesis of Compound (ZC)

3.79 parts of the compound (ZC-2), 20.00 parts of tetrahydrofuran, and 5.99 parts of pyridine were mixed while stirring at 23 ° C for 30 minutes. The obtained mixture was cooled to 0 °C. While maintaining the same temperature, 14.00 parts of the compound (ZC-1) was added to the mixture over 1 hour. The temperature of the mixture was then raised to about 10 ° C and stirred at the same temperature for 1 hour. To the thus obtained reactant containing the compound (ZC-3), 14.51 parts of the compound (ZC-4) (1-(3-dimethylaminopropyl)-3-ethylcarbodiimide salt was added. The acid salt) and 9.97 parts of the compound (ZC-5) were stirred at 23 ° C for 3 hours. 250 parts of ethyl acetate and 16.57 parts of a 5% hydrochloric acid solution were added to the obtained reactant solution, and stirred at 23 ° C for 30 minutes. Then, after standing to separate the layers, the obtained solution was separated to recover the organic layer. 65 parts of saturated sodium hydrogencarbonate was added to the recovered organic layer, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, and then separated to wash the organic layer. Repeat this cleaning operation twice. To the organic layer after washing, 100 parts of ion-exchanged water was added, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, and then separated, and the organic layer was washed with water. Repeat the operation of washing with water 5 times. The obtained organic layer was concentrated, and then the obtained concentrate was fractionated by a column (condition: a fixed phase of a silica gel of 60 to 200 mesh manufactured by Merck, n-heptane/ethyl acetate as a developing solvent) to give 11.60. Parts of the compound (ZC).

MS (mass spectrometry): 422.1 (molecular ion peak)

Synthesis Example 14: Synthesis of Compound (ZD)

3.79 parts of the compound (ZD-2), 20.00 parts of tetrahydrofuran, and 5.99 parts of pyridine were mixed while stirring at 23 ° C for 30 minutes. The obtained mixture was cooled to 0 °C. While maintaining the same temperature, 14.00 parts of the compound (ZD-1) was added to the mixture over 1 hour. The temperature of the mixture was then raised to about 10 ° C, and the mixture was stirred at the same temperature for 1 hour. To the thus obtained reactant containing the compound (ZD-3), 14.51 parts of the compound (ZD-4) (1-(3-dimethylaminopropyl)-3-ethylcarbodiimide salt was added. The acid salt) and 11.74 parts of the compound (ZD-5) were stirred at 23 ° C for 3 hours. 300 parts of ethyl acetate and 16.57 parts of a 5% hydrochloric acid solution were added to the obtained reactant solution, and stirred at 23 ° C for 30 minutes. The obtained solution was allowed to stand for stratification, which was then separated and the organic layer was recovered. 65 parts of saturated sodium hydrogencarbonate was added to the recovered organic layer, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, and then separated to wash the organic layer. Repeat this cleaning operation twice. To the organic layer after washing, 100 parts of ion-exchanged water was added, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, and then separated, and the organic layer was washed with water. Repeat the operation of washing with water 5 times. The obtained organic layer was concentrated, and then the obtained concentrate was fractionated by a column (condition: a fixed phase of a silica gel of 60 to 200 mesh manufactured by Merck, n-heptane / ethyl acetate as a developing solvent) to give 15.49. Part of the compound (ZD).

MS (mass spectrometry): 450.2 (molecular ion peak)

Synthesis Example 15: Synthesis of Compound (ZE)

27.34 parts of the compound (ZE-2), 190.00 parts of methyl isobutyl ketone, and 18.00 parts of pyridine were mixed while stirring at 23 ° C for 30 minutes. The obtained mixture was cooled to 0 °C. While maintaining the same temperature, 48.50 parts of the compound (ZE-1) was added to the mixture over 1 hour. The temperature of the mixture was then raised to about 5 ° C, and the mixture was stirred at the same temperature for 1 hour. The reactant thus obtained was added to 570 parts of ethyl acetate, 99.68 parts of a 5% hydrochloric acid solution, and 126 parts of ion-exchanged water to obtain a mixture, and the mixture was stirred at 23 ° C for 30 minutes. The obtained solution was allowed to stand for stratification, followed by separation to recover the organic layer. To the organic layer, 86.50 parts of a 10% aqueous potassium carbonate solution was added, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, and then separated to wash the organic layer. This cleaning operation was repeated twice. 157 parts of ion-exchanged water was added to the recovered organic layer, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, and then separated, and the organic layer was washed with water. Repeat the operation of washing with water 5 times. The obtained organic layer was concentrated to give 23.89 parts of compound (ZE).

MS (mass spectrometry): 340.1 (molecular ion peak)

Synthesis Example 16: Synthesis of Compound (ZF)

6.32 parts of the compound (ZF-2), 30.00 parts of tetrahydrofuran, and 5.99 parts of pyridine were mixed while stirring at 23 ° C for 30 minutes. The obtained mixture was cooled to 0 °C. While maintaining the same temperature, 14.00 parts of the compound (ZF-1) was added to the mixture over 1 hour. The temperature of the mixture was then raised to about 10 ° C and the mixture was stirred at the same temperature for 1 hour. To the thus obtained reactant containing the compound (ZF-3), 14.51 parts of the compound (ZF-4) (1-(3-dimethylaminopropyl)-3-ethylcarbodiimide salt was added. The acid salt) and 11.74 parts of the compound (ZF-5) were stirred at 23 ° C for 3 hours. 300 parts of ethyl acetate and 16.57 parts of a 5% hydrochloric acid solution were added to the obtained reactant solution, and stirred at 23 ° C for 30 minutes. The obtained solution was allowed to stand for stratification, and then it was separated to recover an organic layer. 65 parts of saturated sodium hydrogencarbonate was added to the recovered organic layer, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, and then separated to wash the organic layer. This cleaning operation was repeated twice. To the organic layer after washing, 100 parts of ion-exchanged water was added, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, and then separated, and the organic layer was washed with water. Repeat the operation of washing with water 5 times. The obtained organic layer was concentrated, and then the obtained concentrate was fractionated by a column (condition: a fixed phase of a silica gel of 60 to 200 mesh manufactured by Merck, n-heptane / ethyl acetate as a developing solvent) to give 16.89 Parts of the compound (ZF).

MS (mass spectrometry): 490.2 (molecular ion peak)

Synthesis Example 17: Synthesis of Compound (ZG)

6.32 parts of the compound (ZF-2), 30.00 parts of tetrahydrofuran, and 5.99 parts of pyridine were mixed while stirring at 23 ° C for 30 minutes. The obtained mixture was cooled to 0 °C. While maintaining the same temperature, 14.00 parts of the compound (ZG-1) was added to the mixture over 1 hour. The temperature of the mixture was then raised to about 10 ° C, and the mixture was stirred at the same temperature for 1 hour. To the thus obtained reactant containing the compound (ZG-3), 14.51 parts of the compound (ZG-4) (1-(3-dimethylaminopropyl)-3-ethylcarbodiimide salt was added. The acid salt) and 9.97 parts of the compound (ZG-5) were stirred at 23 ° C for 3 hours. 300 parts of ethyl acetate and 16.57 parts of a 5% hydrochloric acid solution were added to the obtained reactant solution, and stirred at 23 ° C for 30 minutes. The obtained solution was allowed to stand for stratification, and then, it was separated and the organic layer was recovered. 65 parts of saturated sodium hydrogencarbonate was added to the recovered organic layer, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, and then separated to wash the organic layer. This cleaning operation was repeated twice. To the organic layer after washing, 100 parts of ion-exchanged water was added, and the obtained solution was stirred at 23 ° C for 30 minutes, allowed to stand for separation, and then separated, and the organic layer was washed with water. Repeat the operation of washing with water 5 times. The obtained organic layer was concentrated, and then the obtained concentrate was fractionated by a column (condition: a fixed phase of a silica gel of 60 to 200 mesh manufactured by Merck, n-heptane / ethyl acetate as a developing solvent) to give 19.85. Parts of the compound (ZG).

MS (mass spectrometry): 462.2 (molecular ion peak)

Resin synthesis example

The single system for the synthetic resin is as shown below.

These monomers are referred to as "monomer (A)" to "monomer (Z)" and "monomer (ZA)" to "monomer (ZG)".

Synthesis Example 18: Synthetic Resin A1

Monomer (E), monomer (F), monomer (G), monomer (H), and monomer (I) in a molar ratio of monomer (E): monomer (F): monomer ( G): monomer (H): monomer (I) = 40:10:17:30:3 mixed, and will be two The alkane was added thereto in an amount equivalent to 1.5 times the total weight of the monomers to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as starting agents in an amount of 1 mol% and 3 mol%, respectively, based on the amount of all monomers. The resulting solution was heated and the resulting mixture was heated at 75 ° C for 5 hours. Thereafter, the obtained reaction mixture was poured into a large amount of a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The resin thus obtained is dissolved in the other two The solution was obtained in an alkane, and the solution was poured into a mixture of methanol and ion-exchanged water to precipitate a resin. The resulting resin was filtered. The procedure described in the last two sentences was repeated twice to yield a copolymer having a yield of 60% and a weight average molecular weight of about 7,700. This copolymer has a structural unit derived from a monomer of the following formula, which is referred to as Resin A1.

Synthesis Example 19: Synthetic Resin A2

Monomer (E), monomer (F), monomer (G), monomer (H), and monomer (J) in a molar ratio of monomer (E): monomer (F): monomer ( G): monomer (H): monomer (J) = 38:10:17:30:5 is mixed, and will be equivalent to 1.5 times the total weight of the monomer An alkane is added thereto to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as starting agents in an amount of 1 mol% and 3 mol%, respectively, based on the amount of all monomers. The resulting solution was heated and the resulting mixture was heated at 75 ° C for 5 hours. Thereafter, the obtained reaction mixture was poured into a large amount of a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The resin thus obtained is dissolved in the other two The solution was obtained in an alkane, and the solution was poured into a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The procedure described in the last two sentences was repeated twice to yield a copolymer having a yield of 59% and a weight average molecular weight of about 8,000. This copolymer has a structural unit derived from a monomer of the following formula, which is referred to as Resin A2.

Synthesis Example 20: Synthetic Resin A3

The monomer (I) and the monomer (L) are mixed in a molar ratio of the monomer (I): monomer (L) = 50:50, and the amount corresponding to the total weight of the monomer is 1.5 times An alkane is added thereto to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as starting agents in an amount of 0.7 mol% and 2.1 mol%, respectively, based on the total monomers. To the obtained solution, and the resulting mixture was heated at 75 ° C for 5 hours. Thereafter, the obtained reaction mixture was poured into a large amount of a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The resin thus obtained is dissolved in the other two The solution was obtained in an alkane, and the solution was poured into a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The procedure described in the last two sentences was repeated twice to yield a copolymer having a yield of 68% and a weight average molecular weight of about 16,000. This copolymer has a structural unit derived from a monomer of the formula, referred to as Resin A3.

Synthesis Example 21: Synthetic Resin A4

The monomer (I) and the monomer (M) are mixed in a molar ratio of the monomer (I): monomer (M) = 50:50, and the equivalent of 1.5 times the total weight of the monomer. An alkane is added thereto to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as starting agents in an amount of 0.7 mol% and 2.1 mol%, respectively, based on the total monomers. The resulting solution was heated to 75 ° C for 5 hours. Thereafter, the obtained reaction mixture was poured into a large amount of a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The resin thus obtained is dissolved in the other two The solution was obtained in an alkane, and the solution was poured into a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The procedure described in the last two sentences was repeated twice to yield a copolymer having a yield of 68% and a weight average molecular weight of about 17,000. This copolymer has a structural unit derived from a monomer of the following formula, which is referred to as Resin A4.

Synthesis Example 22: Synthetic Resin A5

Monomer (I) and monomer (N) are mixed in a molar ratio of monomer (I): monomer (N) = 80:20, and will be equivalent to 1.5 times the total weight of the monomer. An alkane is added thereto to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as starting agents in an amount of 0.7 mol% and 2.1 mol%, respectively, based on the total monomers. To the obtained solution, and the resulting mixture was heated at 75 ° C for 5 hours. Thereafter, the obtained reaction mixture was poured into a large amount of a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The resin thus obtained is dissolved in the other two The solution was obtained in an alkane, and the solution was poured into a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The procedure described in the last two sentences was repeated twice to yield a copolymer having a yield of 62% and a weight average molecular weight of about 17,000. This copolymer has a structural unit derived from a monomer of the following formula, which is referred to as Resin A5.

Synthesis Example 23: Synthetic Resin A6

Monomer (E), monomer (K), monomer (F), monomer (H), and monomer (G) in a molar ratio of monomer (E): monomer (K): monomer ( F): monomer (H): monomer (G) = 32:7:8:10:43 is mixed, and will be equivalent to 1.5 times the total weight of the monomer An alkane is added thereto to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as an initiator in an amount of 1 mol% and 3 mol%, respectively, based on the total monomers. To the obtained solution, and the resulting mixture was heated at 73 ° C for 5 hours. Thereafter, the obtained reaction mixture was poured into a large amount of a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The resin thus obtained is dissolved in the other two The solution was obtained in an alkane, and the solution was poured into a mixture of methanol and ion-exchanged water to precipitate a resin. The resulting resin was filtered. The procedure described in the last two sentences was repeated twice to yield a copolymer having a yield of 78% and a weight average molecular weight of about 8900. This copolymer has a structural unit derived from a monomer of the following formula, which is referred to as Resin A6.

Synthesis Example 24: Synthetic Resin A7

The monomer (A), the monomer (B), and the monomer (C) are mixed in a molar ratio of the monomer (A): monomer (B): monomer (C) = 36:34:30, and Will be equivalent to 1.5 times the total weight of the monomer An alkane is added thereto to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as starting agents in an amount of 1.5 mol% and 4.5 mol%, respectively, based on the total monomers. To the obtained solution, and the resulting mixture was heated at 75 ° C for 5 hours. Thereafter, the obtained reaction mixture was poured into a large amount of a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The resin thus obtained is dissolved in the other two The solution was obtained in an alkane, and the solution was poured into a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The procedure described in the last two sentences was repeated twice to yield a copolymer having a yield of 48% and a weight average molecular weight of about 5,000. This copolymer has a structural unit derived from a monomer of the following formula, which is referred to as Resin A7.

Synthesis Example 25: Synthetic Resin A8

The monomer (B) and the monomer (D) are mixed in a molar ratio of the monomer (B): monomer (D) = 70:30, and the amount corresponding to the total weight of the monomer is 1.5 times An alkane is added thereto to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as an initiator in an amount of 1 mol% and 3 mol%, respectively, based on the total monomers. To the obtained solution, and the resulting mixture was heated at 75 ° C for 5 hours. Thereafter, the obtained reaction mixture was poured into a large amount of a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The resin thus obtained is dissolved in the other two The solution was obtained in an alkane, and the solution was poured into a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The procedure described in the last two sentences was repeated twice to yield a copolymer having a yield of 58% and a weight average molecular weight of about 6,700. This copolymer has a structural unit derived from a monomer of the following formula, which is referred to as a specific resin A8.

Synthesis Example 26: Synthetic Resin A9

The monomer (O) and the monomer (L) are mixed in a molar ratio of monomer (O): monomer (L) = 70:30, and will be equivalent to 1.5 times the total weight of the monomer. An alkane is added thereto to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as starting agents in an amount of 0.7 mol% and 2.1 mol%, respectively, based on the total monomers. To the obtained solution, and the resulting mixture was heated at 75 ° C for 5 hours. Thereafter, the obtained reaction mixture was poured into a large amount of a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The resin thus obtained is dissolved in the other two The solution was obtained in an alkane, and the solution was poured into a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The procedure described in the last two sentences was repeated twice, thus yielding a copolymer having a yield of 78% and having a weight average molecular weight of about 15,000. This copolymer has a structural unit derived from a monomer of the following formula, which is referred to as Resin A9.

Synthesis Example 27: Synthetic Resin A10

The monomer (P) and the monomer (L) are mixed in a molar ratio of monomer (P): monomer (L) = 80:20, and will be equivalent to 1.5 times the total weight of the monomer. An alkane is added thereto to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as starting agents in an amount of 0.7 mol% and 2.1 mol%, respectively, based on the total monomers. To the obtained solution, and the resulting mixture was heated at 75 ° C for 5 hours. Thereafter, the obtained reaction mixture was poured into a large amount of a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The resin thus obtained is dissolved in the other two The solution was obtained in an alkane, and the solution was poured into a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The procedure described in the last two sentences was repeated twice to yield a copolymer having a yield of 82% and a weight average molecular weight of about 16,000. This copolymer has a structural unit derived from a monomer of the following formula, which is referred to as Resin A10.

Synthesis Example 28: Synthetic Resin A11

Use monomer (O), and will be equivalent to 1.5 times the weight of the monomer An alkane is added thereto to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as starting agents in an amount of 0.7 mol% and 2.1 mol%, respectively, based on the amount of the monomers. The resulting solution was heated and the resulting mixture was heated at 75 ° C for 5 hours. Thereafter, the obtained reaction mixture was poured into a large amount of a mixture of methanol and ion-exchanged water to precipitate a resin. The resulting resin was filtered. Dissolve the obtained resin in other two The solution was obtained in an alkane, and the solution was poured into a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The procedure described in the last two sentences was repeated twice to yield a polymer having a yield of 77% and having a weight average molecular weight of about 18,000. This polymer has a structural unit derived from a monomer of the formula, referred to as Resin A11.

Synthesis Example 29: Synthetic Resin A12

Monomer (I) and monomer (P) are mixed in a molar ratio of monomer (I): monomer (P) = 80:20, and will be equivalent to 1.5 times the total weight of the monomer. An alkane is added thereto to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as starting agents in an amount of 0.7 mol% and 2.1 mol%, respectively, based on the total monomers. To the obtained solution, and the resulting mixture was heated at 75 ° C for 5 hours. Thereafter, the obtained reaction mixture was poured into a large amount of a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The resin thus obtained is dissolved in the other two The solution was obtained in an alkane, and the solution was poured into a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The procedure described in the last two sentences was repeated twice to yield a copolymer having a yield of 85% and a weight average molecular weight of about 15,000. This copolymer has a structural unit derived from a monomer of the following formula, which is referred to as Resin A12.

Synthesis Example 30: Synthetic Resin A13

The monomer (O) and the monomer (Q) are mixed in a molar ratio of monomer (O): monomer (Q) = 90:10, and two times the total weight of the monomer is 1.5 times. An alkane is added thereto to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as starting agents in an amount of 0.7 mol% and 2.1 mol%, respectively, based on the total monomers. To the obtained solution, and the resulting mixture was heated at 75 ° C for 5 hours. Thereafter, the obtained reaction mixture was poured into a large amount of a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The resin thus obtained is dissolved in the other two The solution was obtained in an alkane, and the solution was poured into a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The procedure described in the last two sentences was repeated twice to yield a copolymer having a yield of 82% and a weight average molecular weight of about 17,000. This copolymer has a structural unit derived from a monomer of the following formula, which is referred to as Resin A13.

Synthesis Example 31: Synthetic Resin A14

The monomer (O) and the monomer (R) are mixed in a molar ratio of monomer (O): monomer (R) = 90:10, and will be equivalent to 1.5 times the total weight of the monomer. An alkane is added thereto to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as starting agents in an amount of 0.7 mol% and 2.1 mol%, respectively, based on the total monomers. To the obtained solution, and the resulting mixture was heated at 75 ° C for 5 hours. Thereafter, the obtained reaction mixture was poured into a large amount of a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The resin thus obtained is dissolved in the other two The solution was obtained in an alkane, and the solution was poured into a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The procedure described in the last two sentences was repeated twice to yield a copolymer having a yield of 80% and a weight average molecular weight of about 17,000. This copolymer has a structural unit derived from a monomer of the following formula, which is referred to as a specific resin A14.

Synthesis Example 32: Synthetic Resin A15

Monomer (E), monomer (K), monomer (F), monomer (S), and monomer (G) in a molar ratio of monomer (E): monomer (K): monomer ( F): monomer (S): monomer (G) = 32:7:8:10:43 is mixed, and will be equivalent to 1.5 times the total weight of the monomer An alkane is added thereto to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as an initiator in an amount of 1 mol% and 3 mol%, respectively, based on the total monomers. To the obtained solution, and the resulting mixture was heated at 70 ° C for 5 hours. Thereafter, the obtained reaction mixture was poured into a large amount of a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The resin thus obtained is dissolved in the other two The intermediate was taken to obtain a solution, and the solution was poured into a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The procedure described in the last two sentences was repeated twice to yield a copolymer having a yield of 80% and a weight average molecular weight of about 9000. This copolymer has a structural unit derived from a monomer of the following formula, which is referred to as Resin A15.

Synthesis Example 33: Synthetic Resin A16

Monomer (E), monomer (T), monomer (F), monomer (S), and monomer (G) in a molar ratio of monomer (E): monomer (T): monomer ( F): monomer (S): monomer (G) = 32:7:8:10:43 is mixed, and will be equivalent to 1.5 times the total weight of the monomer An alkane is added thereto to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as an initiator in an amount of 1 mol% and 3 mol%, respectively, based on the total monomers. To the obtained solution, and the resulting mixture was heated at 70 ° C for 5 hours. Thereafter, the obtained reaction mixture was poured into a large amount of a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The resin thus obtained is dissolved in the other two The solution was obtained in an alkane, and the solution was poured into a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The procedure described in the last two sentences was repeated twice to yield a 76% yield copolymer having a weight average molecular weight of about 8700. This copolymer has a structural unit derived from a monomer of the following formula, which is referred to as Resin A16.

Synthesis Example 34: Synthetic Resin A17

Monomer (W), monomer (K), monomer (F), monomer (G), and monomer (U) in a molar ratio of monomer (W): monomer (K): monomer ( F): monomer (G): monomer (U) = 35:10:6:37:12 is mixed, and will be equivalent to 1.5 times the total weight of the monomer An alkane is added thereto to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as an initiator in an amount of 1 mol% and 3 mol%, respectively, based on the total monomers. To the obtained solution, and the resulting mixture was heated at 75 ° C for 5 hours. Thereafter, the obtained reaction mixture was poured into a large amount of a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The resin thus obtained is dissolved in the other two The solution was obtained in an alkane, and the solution was poured into a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The procedure described in the last two sentences was repeated twice to yield a copolymer having a yield of 65% and a weight average molecular weight of about 7,200. This copolymer has a structural unit derived from a monomer of the following formula, which is referred to as Resin A17.

Synthesis Example 35: Synthetic Resin A18

Monomer (W), monomer (K), monomer (F), monomer (H), monomer (G), and monomer (U) in a molar ratio of monomer (W): monomer ( K): monomer (F): monomer (H): monomer (G): monomer (U) = 35:10:8:12:23:12 is mixed, and will be equivalent to the total weight of the monomer 1.5 Two of the second An alkane is added thereto to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as an initiator in an amount of 1 mol% and 3 mol%, respectively, based on the total monomers. To the obtained solution, and the resulting mixture was heated at 75 ° C for 5 hours. Thereafter, the obtained reaction mixture was poured into a large amount of a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The resin thus obtained is dissolved in the other two The solution was obtained in an alkane, and the solution was poured into a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The procedure described in the last two sentences was repeated twice to yield a 66% yield copolymer having a weight average molecular weight of about 7400. This copolymer has a structural unit derived from a monomer of the following formula, referred to as Resin A18.

Synthesis Example 36: Synthetic Resin A19

Monomer (E), monomer (K), monomer (F), monomer (G), and monomer (U) in a molar ratio of monomer (E): monomer (K): monomer ( F): monomer (G): monomer (U) = 32:7:8:43:10 is mixed, and will be equivalent to 1.5 times the total weight of the monomer An alkane is added thereto to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as an initiator in an amount of 1 mol% and 3 mol%, respectively, based on the total monomers. To the obtained solution, and the resulting mixture was heated at 75 ° C for 5 hours. Thereafter, the obtained reaction mixture was poured into a large amount of a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The resin thus obtained is dissolved in the other two A solution is obtained in the alkane, and the solution is poured into a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The procedure described in the last two sentences was repeated twice to yield a copolymer having a yield of 78% and a weight average molecular weight of about 7,500. This copolymer has a structural unit derived from a monomer of the following formula, which is referred to as Resin A19.

Synthesis Example 37: Synthetic Resin A20

Monomer (A), monomer (G), and monomer (F) are mixed in a molar ratio of monomer (A): monomer (G): monomer (F) = 35:45:20, and Will be equivalent to 1.5 times the total weight of the monomer An alkane is added thereto to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as starting agents in an amount of 1.5 mol% and 4.5 mol%, respectively, based on the total monomers. To the obtained solution, and the resulting mixture was heated at 75 ° C for 5 hours. Thereafter, the obtained reaction mixture was poured into a large amount of a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The resin thus obtained is dissolved in the other two The solution was obtained in an alkane, and the solution was poured into a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The procedure described in the last two sentences was repeated twice to yield a copolymer having a yield of 75% and a weight average molecular weight of about 7000. This copolymer has a structural unit derived from a monomer of the following formula, which is referred to as Resin A20.

Synthesis Example 38: Synthetic Resin A21

The monomer (V) and the monomer (A) are mixed in a molar ratio of monomer (V): monomer (A) = 80:20, and will be equivalent to 1.5 times the total weight of the monomer. An alkane is added thereto to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as starting agents in an amount of 0.5 mol% and 1.5 mol%, respectively, based on the total monomers. To the obtained solution, and the resulting mixture was heated at 75 ° C for 5 hours. Thereafter, the obtained reaction mixture was poured into a large amount of a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The resin thus obtained is dissolved in the other two The solution was obtained in an alkane, and the solution was poured into a mixture of methanol and ion-exchanged water to precipitate a resin. The resulting resin was filtered. The procedure described in the last two sentences was repeated twice, thus yielding a 70% yield copolymer having a weight average molecular weight of about 28,000. This copolymer has a structural unit derived from a monomer of the following formula and is referred to as Resin A21.

Synthesis Example 39: Synthetic Resin A22

Monomer (W), monomer (F), monomer (G), and monomer (S) in a molar ratio of monomer (W): monomer (F): monomer (G): monomer ( S) = 51.7: 7.8: 23.3: 17.2 is mixed, and will be equivalent to 1.5 times the total weight of the monomer An alkane is added thereto to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as an initiator in an amount of 1 mol% and 3 mol%, respectively, based on the total monomers. Therein, and the resulting mixture was heated at 75 ° C for 5 hours. Thereafter, the obtained reaction mixture was poured into a large amount of a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The resin thus obtained is dissolved in the other two The solution was obtained in an alkane, and the solution was poured into a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The procedure described in the last two sentences was repeated twice, thus yielding a copolymer having a yield of 64% and having a weight average molecular weight of about 7,700. This copolymer has a structural unit derived from a monomer of the following formula, which is referred to as Resin A22.

Synthesis Example 40: Synthetic Resin A23

Use monomer (I), and will be equivalent to 1.5 times the weight of the monomer An alkane is added thereto to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as starting agents in an amount of 0.7 mol% and 2.1 mol%, respectively, based on the amount of the monomers. The resulting solution was heated and the resulting mixture was heated at 75 ° C for 5 hours. Thereafter, the obtained reaction mixture was poured into a large amount of a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The resin thus obtained is dissolved in the other two The solution was obtained in an alkane, and the solution was poured into a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The procedure described in the last two sentences was repeated twice to yield a polymer having a yield of 83% and a weight average molecular weight of about 19,000. This polymer has a structural unit derived from a monomer of the formula, referred to as Resin A23.

Synthesis Example 41: Synthetic Resin A24

Use monomer (X), and will be equivalent to 1.5 times the weight of the monomer An alkane is added thereto to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as starting agents in an amount of 0.7 mol% and 2.1 mol%, respectively, based on the amount of the monomers. The resulting solution was heated and the resulting mixture was heated at 75 ° C for 5 hours. Thereafter, the obtained reaction mixture was poured into a large amount of a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The resin thus obtained is dissolved in the other two The solution was obtained in an alkane, and the solution was poured into a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The procedure described in the last two sentences was repeated twice to yield a polymer having a yield of 85% and having a weight average molecular weight of about 20,000. This polymer has a structural unit derived from a monomer of the formula, referred to as Resin A24.

Synthesis Example 42: Synthetic Resin A25

Use monomer (Y), and will be equivalent to 1.5 times the weight of the monomer An alkane is added thereto to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as starting agents in an amount of 0.7 mol% and 2.1 mol%, respectively, based on the amount of the monomers. Therein, and the resulting mixture was heated at 75 ° C for 5 hours. Thereafter, the obtained reaction mixture was poured into a large amount of a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The resin thus obtained is dissolved in the other two The solution was obtained in an alkane, and the solution was poured into a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The procedure described in the last two sentences was repeated twice to yield a polymer having a yield of 83% and a weight average molecular weight of about 19,000. This polymer has a structural unit derived from a monomer of the following formula, which is referred to as a designated resin A25.

Synthesis Example 43: Synthetic Resin A26

Use monomer (Z), and will be equivalent to 1.5 times the weight of the monomer An alkane is added thereto to obtain a solution. The amount of azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) was added as an initiator to the amount of 0.7 mol% and 2.1 mol%, respectively, based on the amount of the monomer. And the resulting mixture was heated at 75 ° C for 5 hours. Thereafter, the obtained reaction mixture was poured into a large amount of a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The resin thus obtained is dissolved in the other two The solution was obtained in an alkane, and the solution was poured into a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The procedure described in the last two sentences was repeated twice to yield a polymer having a yield of 81% and having a weight average molecular weight of about 21,000. This polymer has a structural unit derived from a monomer of the formula, referred to as Resin A26.

Synthesis Example 44: Synthetic Resin A27

Use monomer (ZA), and will be equivalent to 1.5 times the weight of the monomer An alkane is added thereto to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as starting agents in an amount of 0.7 mol% and 2.1 mol%, respectively, based on the amount of the monomers. The resulting solution was heated and the resulting mixture was heated at 75 ° C for 5 hours. Thereafter, the obtained reaction mixture was poured into a large amount of a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The resin thus obtained is dissolved in the other two The solution was obtained in an alkane, and the solution was poured into a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The procedure described in the last two sentences was repeated twice, thus yielding a 78% yield polymer having a weight average molecular weight of about 18,000. This polymer has a structural unit derived from a monomer of the formula, referred to as Resin A27.

Synthesis Example 45: Synthetic Resin A28

Use monomer (ZB), and will be equivalent to 1.5 times the weight of the monomer An alkane is added thereto to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as starting agents in an amount of 0.7 mol% and 2.1 mol%, respectively, based on the amount of the monomers. The resulting solution was heated and the resulting mixture was heated at 75 ° C for 5 hours. Thereafter, the obtained reaction mixture was poured into a large amount of a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The resin thus obtained is dissolved in the other two The solution was obtained in an alkane, and the solution was poured into a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The procedure described in the last two sentences was repeated twice, thus yielding a 73% yield polymer having a weight average molecular weight of about 19,000. This polymer has a structural unit derived from a monomer of the formula, referred to as Resin A28.

Synthesis Example 46: Synthetic Resin A29

Use monomer (ZC), and will be equivalent to 1.5 times the weight of the monomer An alkane is added thereto to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as starting agents in an amount of 0.7 mol% and 2.1 mol%, respectively, based on the amount of the monomers. The resulting solution was heated and the resulting mixture was heated at 75 ° C for 5 hours. Thereafter, the obtained reaction mixture was poured into a large amount of a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The resin thus obtained is dissolved in the other two The solution was obtained in an alkane, and the solution was poured into a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The procedure described in the last two sentences was repeated twice to yield a 71% yield polymer having a weight average molecular weight of about 16,000. This polymer has a structural unit derived from a monomer of the formula, referred to as Resin A29.

Synthesis Example 47: Synthetic Resin A30

Use monomer (ZD), and will be equivalent to 1.5 times the weight of the monomer An alkane is added thereto to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as starting agents in an amount of 0.7 mol% and 2.1 mol%, respectively, based on the amount of the monomers. The resulting solution was heated and the resulting mixture was heated at 75 ° C for 5 hours. Thereafter, the obtained reaction mixture was poured into a large amount of a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The resin thus obtained is dissolved in the other two The solution was obtained in an alkane, and the solution was poured into a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The procedure described in the last two sentences was repeated twice to yield a polymer having a yield of 69% and having a weight average molecular weight of about 16,000. This polymer has a structural unit derived from a monomer of the formula, referred to as Resin A30.

Synthesis Example 48: Synthetic Resin A31

Use monomer (ZE), and will be equivalent to 1.5 times the weight of the monomer An alkane is added thereto to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as starting agents in an amount of 0.7 mol% and 2.1 mol%, respectively, based on the amount of the monomers. The resulting solution was heated and the resulting mixture was heated at 75 ° C for 5 hours. Thereafter, the obtained reaction mixture was poured into a large amount of a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The resin thus obtained is dissolved in the other two The solution was obtained in an alkane, and the solution was poured into a mixture of methanol and water to precipitate a resin. The resulting resin was filtered. The procedure described in the last two sentences was repeated twice to yield a polymer having a yield of 76% and having a weight average molecular weight of about 18,000. This polymer has a structural unit derived from a monomer of the following formula, which is referred to as Resin A31.

Synthesis Example 49: Synthetic Resin A32

Use monomer (ZF), and will be equivalent to 1.5 times the weight of the monomer An alkane is added thereto to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as starting agents in an amount of 0.7 mol% and 2.1 mol%, respectively, based on the amount of the monomers. The resulting solution was heated and the resulting mixture was heated at 75 ° C for 5 hours. Thereafter, the obtained reaction mixture was poured into a large amount of a mixture of methanol and ion-exchanged water to precipitate a resin. The resulting resin was filtered. The resin thus obtained is dissolved in the other two The solution was obtained in an alkane, and the solution was poured into a mixture of methanol and ion-exchanged water to precipitate a resin. The resulting resin was filtered. The procedure described in the last two sentences was repeated twice, thus yielding a 70% yield polymer having a weight average molecular weight of about 17,000. This polymer has a structural unit derived from a monomer of the formula, referred to as Resin A32.

Synthesis Example 50: Synthetic resin A33

Use monomer (ZG), and will be equivalent to 1.5 times the weight of the monomer An alkane is added thereto to obtain a solution. Azobisisobutyronitrile and azobis(2,4-dimethylvaleronitrile) were added as starting agents in an amount of 0.7 mol% and 2.1 mol%, respectively, based on the amount of the monomers. The resulting solution was heated and the resulting mixture was heated at 75 ° C for 5 hours. Thereafter, the obtained reaction mixture was poured into a large amount of a mixture of methanol and ion-exchanged water to precipitate a resin. The resulting resin was filtered. The resin thus obtained is dissolved in the other two The solution was obtained in an alkane, and the solution was poured into a mixture of methanol and ion-exchanged water to precipitate a resin. The resulting resin was filtered. The procedure described in the last two sentences was repeated twice, thus yielding a 76% yield polymer having a weight average molecular weight of about 18,000. This polymer has a structural unit derived from a monomer of the formula, referred to as Resin A33.

(Preparation of a resist composition)

The resist composition was prepared by mixing and dissolving the respective compositions shown in Table 1, followed by filtration through a fluororesin filter having a pore size of 0.2 μm.

<Resin>

A1 to A33: Resin A1 to Resin A33 prepared by the synthesis examples

<acid generator>

Acid generator B1:

Acid generator B2:

Acid generator B3:

Acid generator B4:

Acid generator B5:

<quenching agent>

C1: 2,6-diisopropylaniline,

<solvent>

Propylene glycol monomethyl ether acetate 265.0 parts

Propylene glycol monomethyl ether 20.0 parts

2-heptanone 20.0 parts

Γ-butyrolactone 3.5 parts

(evaluation of defects)

The above-described resist composition was applied to each of the 12-inch crucible wafers by spin coating, and the thickness of the film produced after drying became 150 nm.

The obtained wafer was prebaked in a direct heating plate at a temperature shown in the "PB" column of Table 1 for 60 seconds to obtain a composition layer.

The wafer having the manufactured composition layer thus obtained was gently rinsed with water for 60 seconds using a developing device (ACT-12, Tokyo electron Co. Ltd.).

Thereafter, the number of defects was counted using a defect detecting device (KLA-2360, KLA-Tencor Co. Ltd.).

The results are shown in Table 2.

(manufacturing resist pattern 1)

A composition of an organic anti-reflection film ("ARC-29", manufactured by Nissan Chemical Co. Ltd.) was coated on a ruthenium wafer and baked at 205 ° C for 60 seconds to form an organic resistance of 78 nm in thickness on each of the ruthenium wafers. Reflective film.

Next, the above-mentioned resist composition was applied thereto by spin coating so that the thickness of the resulting composition layer became 85 nm after drying.

The obtained wafer was prebaked on a direct hot plate at a temperature indicated by the "PB" column in Table 1 for 60 seconds to form a composition layer.

The contact pattern was exposed using a mask pattern (pitch: 100 nm, hole diameter: 70 nm) for use in infiltration lithography ("XT: 1900Gi" by ASML Ltd.: NA = 1.35, 3/42 annularX-Y The ArF-excited laser stepper of polarization) forms a composition layer on the wafer by gradually changing the exposure amount. Ultrapure water is used as a medium for infiltration.

After the exposure, post-exposure baking was performed for 60 seconds at the temperature indicated by the "PEB" column in Table 1.

Then, paddle derelopment was performed for 60 seconds with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide to obtain a resist pattern.

(Evaluating the mask error factor (MEF))

A resist pattern formed using a mask in which the mask sizes of the line patterns are 48 nm, 50 nm, and 52 nm, respectively. The pitch of the mask is 100 nm. The exposure amount was set to a degree that the line pattern was 50 nm wide by using a line and pitch pattern of 1:1 (mask size of line pattern: 50 nm, pitch width: 100 nm).

The obtained results were plotted on the horizontal axis with the mask size set, and the line width of the line pattern formed using the mask as the vertical axis, and the slope of the regression line obtained from each chart was taken as the MEF.

The results are shown in Table 2.

The resist compositions of the present invention (Examples 1 to 34) can be used as a resist pattern having less defects, and it is possible to achieve an excellent MEF when a resist pattern is produced.

Meanwhile, by comparing Example 1, when the resist pattern was produced, the obtained resist pattern had a large number of defects and a poor MEF.

(Evaluation Focus Limit (DOF))

Each of the resist patterns was produced according to the resist composition using a mask pattern (hole pitch: 100 nm, pore diameter: 70 nm). An exposure amount in which a 55 nm hole diameter can be achieved in the pattern is defined as effective sensitivity.

The index (DOF) was measured while the pore diameter of the resist pattern was maintained at a focus range of 55 nm ± 5% (52.5 to 57.5 nm), wherein the resist pattern was formed according to the effective sensitivity while gradually adjusting the coke.

The results are shown in Table 3.

According to the resist composition of the present invention, when a resist pattern is produced, a resist pattern having a good DOF (wide DOF) and MEF, and a pattern having less defects can be produced. Therefore, the resist composition of the present invention can be used for semiconductor micromachining.

Claims (3)

A resist composition comprising: a resin having a structural unit derived from a compound represented by the formula (a); and an acid generator, Wherein R ¹ represents a hydrogen atom or a methyl group; R ² represents a C ₁ to C ₁₈ aliphatic hydrocarbon group having a halogen atom or a group represented by the formula (a-g2); -A ¹³ -X ¹² -A ¹⁴ (a-g2) Wherein A ¹³ represents a C ₃ to C ₁₇ aliphatic hydrocarbon group having a halogen atom as needed; X ¹² represents a carbonyloxy group or an oxycarbonyl group; and A ¹⁴ represents a C ₃ to C ₁₇ aliphatic hydrocarbon group having a halogen atom as needed; , A ¹³ , A ¹⁴ and X ^{12 have a} total number of carbon atoms of 17 or less; one or both of A ¹³ and A ¹⁴ have a halogen atom; and A ¹ represents an optionally substituted C ₁ to C ₆ alkanediyl group or a base of the formula (a-g1); Wherein s represents 0 or 1; A ¹⁰ and A ¹² independently represent an optionally substituted C ₁ to C ₅ aliphatic hydrocarbon group; A ¹¹ represents a single bond or an optionally substituted C ₁ to C ₅ aliphatic hydrocarbon group; X ¹⁰ And X ¹¹ independently represents an oxygen atom, a carbonyl group, a carbonyloxy group or an oxycarbonyl group; however, the total number of carbon atoms of A ¹⁰ , A ¹¹ , A ¹² , X ¹⁰ and X ¹¹ is 6 or less. The resist composition according to claim 1, wherein the solvent is further contained. A method for producing a resist pattern, comprising the steps of: (1) applying a resist composition according to claim 1 of the patent application to a substrate; and (2) drying the applied composition to form a composition layer; (3) exposing the composition layer using an exposure device; (4) heating the exposed composition layer; and (5) developing the heated composition layer using a developing device.